WO2011127752A1 - 由co气相法制备草酸酯的方法 - Google Patents
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- C07C67/18—Preparation of carboxylic acid esters by conversion of a group containing nitrogen into an ester group
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- B01J21/04—Alumina
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
Definitions
- the invention relates to a method for preparing oxalate by CO gas phase method, in particular to a CO coupling preparation of dinonyl oxalate, co-production of diethyl oxalate, dipropyl oxalate or dibutyl oxalate, and greatly reducing nitrogen
- Oxalate is an important organic chemical raw material, which is widely used in fine chemicals to produce various dyes, medicines, important solvents, extractants and various intermediates.
- oxalate has received extensive international attention as a biodegradable environmentally friendly engineering plastic monomer.
- oxalate can be hydrolyzed at atmospheric pressure to obtain oxalic acid, and atmospheric pressure ammonia solution can obtain high-quality slow-acting fertilizer oxalyl ammonia.
- Oxalate can also be used as a solvent and in the production of pharmaceutical and dye intermediates and the like, for example, various condensation reactions with fatty acid esters, cyclohexylacetophenone, amino alcohols, and many heterocyclic compounds.
- ethylene glycol is mainly produced by petroleum route, and the cost is high. China needs a large amount of imported ethylene glycol every year. In 2007, the import volume was nearly 480. Ten thousand tons.
- the traditional oxalate production method is prepared by esterification reaction of oxalic acid with an alcohol.
- the method has high production process cost, high energy consumption, serious pollution, and unreasonable utilization of raw materials.
- people have been looking for a low-cost, environmentally friendly process route.
- United Oil Corporation DFFenton discovered that carbon monoxide, alcohol and oxygen can directly synthesize dialkyl oxalate by oxidative carbonylation. Since then, Ube Industries of Japan and ARCO of the United States have successively carried out in this field. Research and development work.
- the synthesis of oxalate by carbon monoxide oxidative coupling method can be divided into liquid phase method and gas phase method.
- the liquid phase synthesis of oxalate by carbon monoxide is relatively harsh, the reaction is carried out under high pressure, the liquid phase system is easy to corrode equipment, and the catalyst is easily lost during the reaction.
- the gas phase method for CO coupling to prepare oxalate has the most advantages.
- the Japanese Ube Industrial Co., Ltd. and the Italian Monte Edison Company successively carried out gas phase research.
- the gas phase catalytic synthesis oxalate process developed by Ube Industrial Co., Ltd. has a reaction pressure of 0.5 MPa and a temperature of 80 °C to 150 °C.
- NO is derived from ammonia oxidation products or nitric acid tail gas, but in addition to the required NO or NO 2 in the ammonia oxidation product or the nitric acid tail gas, it also contains non-reactive and difficult to condense gases such as N 2 , Ar, He, etc. Gases that are non-reactive and difficult to condense, if they enter the synthetic oxalate system in large amounts, are very unfavorable for the reaction to catalyze the synthesis of oxalate, and may even prevent the reaction from proceeding. Only by discharging these non-reactive gases out of the reaction system can the reaction proceed smoothly.
- Patent CN1048098A uses a combination of compression and condensation to accomplish this.
- the operating conditions required by this patent are harsh and ineffective.
- Patent CN200510107783.4 further improves it, and discloses a new production method for synthesizing NO for oxalate, which firstly absorbs a large amount of nitrite with an alcohol, and then combines compression and condensation, 4 A small amount of alcohol and nitrite in the gas phase of the Ba is condensed into a liquid at a pressure of 0.1 to 10 MPa, and the condensation temperature used is between -20 ° C and 100 ° C to make alcohols and nitrites and non-condensable gases. Separate, and then the recovered condensed liquid is recycled to discharge non-condensable gas.
- this method also has the problem of harsh operating conditions, while operating at high energy consumption and low utilization of nitrogen oxides or nitrites.
- High-gravity technology is a new technology to strengthen the multi-phase flow transmission and reaction process. Since its inception in the last century, it has received extensive attention at home and abroad, due to its wide applicability and the small size and light weight that traditional equipment does not have. Low energy consumption, easy operation, easy maintenance, safety, reliability, flexibility and adaptability to the environment make the super-gravity technology have broad commercial application prospects in the environmental protection, materials and biochemical industries. But the current super gravity technology The technique is still mainly in the application development stage, and the application of a rotating bed supergravity reactor to the production of ⁇ C 4 alkyl nitrite has not been seen in the production of oxalate.
- the technical problem to be solved by the present invention is a technical problem of low utilization of nitrogen oxides or nitrites in the prior literature, and a novel method for preparing oxalate by CO gas phase method.
- This method has the advantage of high utilization of nitrogen oxides or nitrites.
- a method for preparing oxalate by CO gas phase method comprising the following steps:
- Ozone-containing gas stream V is oxidatively esterified with methanol and oxygen into a rotating bed supergravity reactor II to form an effluent VI containing nitroxanolate, which is obtained by separation of methyl nitrite
- the effluent VII and CO gas II enter the coupling reactor II, contact with the catalyst II, and react to form a dimethyl oxalate effluent VIII and a NO-containing gas phase effluent IX, and the resulting dimethyl oxalate effluent VIII is separated to obtain oxalic acid.
- the NO-containing gas phase effluent IX is returned to the c) step, mixed with the NO-containing gas phase stream V;
- the porous bed of the rotating bed supergravity reactor II is fixed with a porous packing layer;
- the catalyst II is a palladium-containing catalyst, and the palladium content is 0.01 to 1% based on the weight of the catalyst carrier.
- the above-mentioned NO-containing gas phase stream V is obtained by steps a) and b) prior to step c) as follows:
- the porous packed bed is fixed to the rotor of the rotating bed supergravity reactor I; the molar ratio of CO gas II to CO gas I is 5 300 : 1 ;
- the palladium-containing catalyst has a monomer content of 0.01 to 1% based on the weight of the catalyst carrier.
- the operating conditions of the rotating bed supergravity reactor I in the above technical solution are preferably: the reaction temperature is 20 ⁇ 100 ° C, the reaction pressure is - 0.05 ⁇ 2.0 MPa, and the reaction contact time is The molar ratio of the 0.05 - 300 oxynitride mixture to the C 2 -C 4 alkanol and oxygen or oxygen in the air is 1:1 -50 : 0.2 0.3; more preferred operating conditions for the rotating bed supergravity reactor I are: The temperature is 30 ⁇ 70 ° C, the reaction pressure is 0.01 ⁇ 1.0 MPa, the reaction contact time is 1 ⁇ 200 seconds, and the molar ratio of nitrogen oxide mixture to C 2 ⁇ C 4 alkanol and oxygen or oxygen in air is 1: 1 ⁇ 20: 0.22-0.28;
- the operating conditions of the rotating bed supergravity reactor II are preferably: reaction temperature is 20 ⁇ 100°C, reaction pressure is -0.05 ⁇ 2.0MPa, reaction contact time is 0.05-300 seconds, including NO The molar ratio of NO to methanol and oxygen
- the more preferable operating conditions of the rotating bed supergravity reactor II are: the reaction temperature is 25 to 70 ° C, the reaction pressure is 0.05 to 1.0 MPa, the reaction contact time is 1 to 200 seconds, and the NO in the NO-containing gas phase V is The molar ratio of methanol to oxygen is 1: 1 ⁇ 20: 0.1 ⁇ 0.25.
- the operating conditions of the coupling reactor I in the above technical solution are preferably: the reaction temperature is 80 to 160 ° C, the reaction contact time is 0.1 to 100 seconds, the reaction pressure is -0.05 to 2.0 MPa, and the CO gas I and C 2 to C
- the molar ratio of 4 -alkyl nitrite is from 1.1 to 15:1; more preferred operating conditions for coupling reactor I are: reaction temperature of 90 to 150 ° C, reaction contact time of 0.5 to 50 seconds, reaction pressure of 0.01 ⁇ l.OMPa, the molar ratio of CO gas I to C 2 ⁇ C 4 alkyl nitrite is 1.1 ⁇ 10: 1;
- the reaction condition of coupling reactor II is preferably: reaction temperature is 80 ⁇ 160 °C, reaction The contact time is 0.1 to 100 seconds, the reaction pressure is -0.05 to 2.0 MPa, and the molar ratio of CO gas II to cerium nitrite effluent VII is 1.1 to 10:1.
- More preferred reaction conditions for the coupling reactor II are: reaction temperature of 90 to 150 ° C, reaction contact time of 0.5 to 50 seconds, reaction pressure of 0.01 to 1.0 MPa, CO gas II and methyl nitrite effluent VII
- the molar ratio is 1.1 ⁇ 5: 1.
- the preferred embodiment of the nitrogen oxide mixture is selected from the group consisting of an ammoxidation product and a tail gas of nitric acid or a reaction of nitrite with sulfuric acid or nitric acid, or a decomposition of nitric acid, and a more preferred embodiment of the nitrogen oxide mixture is selected from the group consisting of an ammoxidation product;
- the C 2 -C 4 alkanol is selected from the group consisting of ethanol, propanol and butanol; the molar ratio of CO gas II to CO gas I is preferably in the range of 10 200: 1.
- the active components of the catalyst I and the catalyst II are both palladium, and the amount of palladium in a single shield is preferably in the range of 0.01 to 0.8% by weight of the catalyst carrier, more preferably in the range of 0.02 to 0.6% by weight of the catalyst carrier;
- Catalyst II further comprises an optional auxiliary agent and a carrier comprising at least one selected from the group consisting of alkali metal, alkaline earth metal or transition metal element compound, and the amount of the elemental metal is 0.01 to 15% by weight of the catalyst, preferably 1 ⁇ 10%, - a '"a,/", ⁇ ⁇ ⁇ & 4 y auxiliaries preferably selected from K, Fe, Bi, Cu, Zr, Ba, Mn, Mg, Ce and SrH dagger at least one compound to The amount of the elemental metal is preferably in the range of 0.05 to 10% by weight of the catalyst, more preferably 1 to 7%; the carrier is at least one selected from the group consisting of alumina, mole
- the combination of compression, condensation and alcohol absorption vents the non-reactive gas, and introduces the decyl nitrite formed by the NO reaction into the system reaction, but the problem is that the decyl nitrite has a low boiling point (-16.5 ° C), It is a gas at normal temperature. Therefore, a combination of compression, condensation, and alcohol absorption is required, resulting in high operating energy consumption and unsatisfactory results.
- ethanol, propanol or butanol is first oxidized with oxygen to form an oxidative reaction with NO.
- Ethyl nitrate, propyl nitrite or butyl nitrite, and the non-reactive inert components introduced into the raw material nitrogen oxides can be directly emptied or further processed by simple separation, at which time the nitrogen oxides in the air are released.
- nitrite can be controlled below the lower content, and then ethyl nitrite (boiling point 15 ° C;), propyl nitrite (boiling point 39 ° C) or butyl nitrite (boiling point 75 ° C)
- the CO gas I is introduced into the coupling reactor I, and a coupling reaction occurs to form diethyl oxalate, dipropyl oxalate or dibutyl oxalate, and the reaction releases NO, and the NO and unreacted CO released by the reaction are newly supplemented.
- the incoming oxygen and sterol enter the reactor II to form decyl nitrite, and then no longer need to be compressed and condensed.
- the coupling reactor II is the main reactor of the coupling reaction process
- the coupling reactor I is the reactor of the NO replenishment system, which plays an auxiliary role, and most of the CO raw materials are
- the reaction of Reactor II produces dinonyl oxalate.
- the study also found that the reaction of oxidative esterification of nitrogen oxides with oxygen and alcohol to form alkyl nitrite is a fast reaction, while the reaction of side reactions to form nitric acid is slightly slower; the reaction rate of NO oxidation and esterification is mainly caused by gas-liquid reaction.
- the effect of the mass resistance if effectively improving the gas-liquid mass transfer efficiency, can further effectively reduce the probability of N 2 0 4 formation, and further reduce the loss of nitrogen oxides or nitrites.
- the technical solution of the present invention fully studies nitrogen oxides and oxygen
- a rotating bed supergravity reactor as an oxidative esterification reactor, which can make full use of the rotating bed supergravity reactor to greatly increase the gas-liquid mass transfer rate.
- the present invention fully utilizes the difference in boiling point of different nitrites, and fully utilizes the rotating bed supergravity
- the advantages of efficient mass transfer of the reactor thereby ensuring high yield and high selectivity of the coupling reaction, while greatly reducing the loss of nitrogen oxides or nitrites, and improving the utilization of nitrogen oxides or nitrites. Reduced pollution to the environment.
- the nitrogen oxide mixture and the C 2 -C 4 alkanol and air are first introduced into the rotating bed supergravity reactor I to form an effluent I containing a C 2 -C 4 alkyl nitrite.
- the effluent is separated to obtain effluent III of non-condensable gas effluent II and c 2 ⁇ c 4 alkyl nitrite; effluent III and CO gas I of said C 2 -C 4 alkyl nitrite
- effluent III and CO gas I of said C 2 -C 4 alkyl nitrite
- the reaction produces an oxalate liquid phase effluent IV and a NO-containing gas phase stream V; the NO-containing gas phase stream V and sterol and oxygen enter the rotating bed supergravity reactor II to oxidize
- the esterification reaction produces an effluent VI containing decyl nitrite.
- the effluent ruthenium nitrite effluent VII and CO gas II obtained after separation enter the coupling reactor II, and contact with the catalyst II to form oxalic acid II.
- the oxime ester effluent VIII and the NO-containing gas phase effluent IX; optionally, the NO-containing gas phase effluent IX is mixed with the NO-containing gas phase stream V for recycling.
- the molar ratio of CO gas II to CO gas I is 10 200:1;
- the nitrogen oxide mixture is selected from the group consisting of ammonia oxidation products;
- the C 2 ⁇ C 4 alkanol is selected from the group consisting of ethanol, propanol and butanol;
- catalyst I and catalyst II Each is selected from the group consisting of palladium-containing catalysts, and the palladium content is 0.01 to 1% based on the weight of the catalyst carrier.
- a porous packing layer is fixed on the rotors of the rotating bed supergravity reactor I and the rotating bed supergravity reactor II.
- the operating conditions of the rotating bed supergravity reactor I are: reaction temperature 30 ⁇ 70 ° C, reaction pressure 0.01 ⁇ l.OMPa, reaction contact time 1 ⁇ 200 seconds, nitrogen oxide mixture and C 2 ⁇ C 4
- the molar ratio of the alkanol to the oxygen or oxygen in the air is 1: 1 ⁇ 50: 0.2 0.3
- the operating conditions of the rotating bed supergravity reactor II are: the reaction temperature is 25 ⁇ 70 ° C, the reaction pressure is 0.05 ⁇ l.
- the reaction contact time is 1 ⁇ 200 seconds
- the molar ratio of NO to the sterol and oxygen in the NO-containing gas phase V is 1: 1 ⁇ 20: 0.1 - 0.25
- the operating condition of the coupled reactor I is: the reaction temperature is 90 ⁇ 150°C, reaction contact time is 0.5 ⁇ 50 seconds, reaction pressure is 0.01 ⁇ l.OMPa, molar ratio of CO gas I to C 2 ⁇ C 4 alkyl nitrite is 1.1 ⁇ 10: 1
- the reaction conditions of the reactor II are: the reaction temperature is 90 to 150 ° C, the reaction contact time is 0.5 to 50 seconds, and the reaction pressure is 0.01 ⁇ 1.0MPa, under the condition that the molar ratio of CO gas II to decyl nitrite effluent VII is 1.1 ⁇ 5: 1, the result is that the utilization rate of NO can be more than 98%, preferably more than 99%, so Good technical results.
- the invention is further illustrated by the following examples, but is not limited
- the NO-containing mixed gas from ammonia oxidation (90 volume of NO, 10% of nitrogen volume) and ethanol and oxygen first enter the rotating bed supergravity reactor I to form effluent I containing ethyl nitrite; After separation, the effluent III of the non-condensable gas (containing N 2 ) effluent II and ethyl nitrite is obtained; the effluent III of ethyl nitrite enters the coupling reactor I with the CO gas I, and is contacted with the catalyst I.
- the reaction produces diethyl oxalate liquid phase effluent IV and NO-containing gas phase stream V; the NO-containing gas phase stream V undergoes oxidative esterification reaction with sterol and oxygen into a rotating bed supergravity reactor II to form an effluent containing methyl nitrite.
- VI the effluent obtained after separation of methyl nitrite VII and CO gas II into the coupling reactor II, contact with the catalyst II, the reaction to form dicaptan oxalate effluent VIII and NO containing gas phase effluent IX;
- the NO-containing gas phase effluent IX is mixed with the NO-containing gas phase stream V for recycling.
- the molar ratio of the CO gas II to the CO gas I is 150:1; the catalyst I and the catalyst II are both selected from the active component of the bar, and the weight composition thereof is: 0.45% Pd + 0.40% K + 0.22% Fe /aA 1 2 0 3 , in the rotating bed, the operating conditions of the supergravity reactor I are: the reaction temperature is 40 ° C, the reaction pressure is O.OlMPa, the reaction contact time is 50 seconds, and the molar ratio of NO to ethanol and oxygen is 1: 20: 0.25; The operating conditions of the rotating bed supergravity reactor II are: reaction temperature is 30 ° C, reaction pressure is O.OlMPa, reaction contact time is 20 seconds, NO and methanol in the NO-containing gas phase V The molar ratio of oxygen is 1: 5 : 0.18; the operating conditions of the coupled reactor I are: reaction temperature is 98 ° C, reaction contact time is 3 seconds, reaction pressure is O.OlMPa, CO gas I and ethyl nit
- Example 1 According to the procedure of Example 1, except that the molar ratio of CO gas II to CO gas I is 100:1; both catalyst I and catalyst II are selected from palladium as an active component, and the weight composition thereof is: 0.30% Pd + 0.2% Bi + 0.02% Fe /a-Al 2 O 3 .
- the C 2 ⁇ C 4 alkanol is selected from the group consisting of ethanol.
- the operating conditions of the rotating bed supergravity reactor I are: reaction temperature 70 ° C, reaction pressure 0.5 MPa, reaction contact time 150 seconds, NO with ethanol and oxygen The molar ratio is 1: 20: 0.26;
- the operating conditions of the rotating bed supergravity reactor II are: reaction temperature is 45 ° C, reaction pressure is 0.4 MPa, reaction contact time is 30 seconds, NO in NO-containing gas phase stream V
- the molar ratio of methanol to oxygen is 1:25:0.20;
- the operating conditions of the coupled reactor I are: reaction temperature is 150 ° C, reaction contact time is 40 seconds, reaction pressure is 0.
- the molar ratio of ethyl nitrate is 5:1; the reaction conditions of coupling reactor II are: reaction temperature is 140 ° C, reaction contact time is 2 seconds, reaction pressure is 0.2 MPa, and CO gas II and decyl nitrite are discharged.
- the molar ratio of the substance VII is 5:1
- the result is that the utilization rate of NO is 99.6%
- the content of nitrogen oxides in the venting tail gas is 25 ppm
- the space-time yield of dinonyl oxalate is 980 g / (hour.
- the selectivity of dinonyl oxalate is 98.6%.
- the weight composition of catalyst I is 0.30% Pd + 0.2% Bi + 0.02% Fe/a-Al 2 O 3 , catalyst II
- the weight composition is 0.6% Pd + 0.2% Cu + 0.08% Fe/a-Al 2 OC 2 ⁇ C 4 alkanol is selected from n-butanol
- the operating conditions in the rotating bed supergravity reactor I are: reaction temperature 50 °C, reaction pressure is -0.02MPa, reaction contact time is 30 seconds, the molar ratio of NO to n-butanol and oxygen is 1:10: 0.27;
- the operating conditions of rotating bed supergravity reactor II are: reaction temperature is 60° C, the reaction pressure is 0.2 MPa, the reaction contact time is 10 seconds, and the molar ratio of NO to sterol and oxygen in the V-containing gas phase V is 1:15: 0.20;
- the operating conditions of the coupled reactor I are: At 130 ° C, the reaction contact time is
- Example 2 According to the procedure of Example 1, except that the molar ratio of CO gas II to CO gas I is 30:1; the weight composition of the catalyst I is 0.8% Pd + 10% Ce + 0.003% Zr + 0.507% Fe/TiO 2 , The weight composition of the catalyst II was 0.6% Pd + 0.2% Cu + 0.08% Fe/a-Al 2 O 3 .
- the C 2 ⁇ C 4 alkanol is selected from n-propanol.
- the operating conditions of the rotating bed supergravity reactor I are: reaction temperature is 60 ° C, reaction pressure is 1.5 MPa, reaction contact time is 5 seconds, NO and positive
- the molar ratio of propanol to oxygen is 1: 5: 0.25
- the operating conditions of the rotating bed supergravity reactor II are: reaction temperature is 45 ° C, reaction pressure is 1.5 MPa, reaction contact time is 3 seconds, and NO-containing gas phase stream V
- the molar ratio of NO to sterol and oxygen is 1:3: 0.23
- the operating conditions of the coupled reactor I are: reaction temperature is 110 ° C, reaction contact time is 2 seconds, reaction pressure is 0.01 MPa, CO gas I
- the molar ratio to propyl nitrite is 8:1
- the reaction conditions of coupling reactor II are: reaction temperature is 125 ° C, reaction contact time is 2 seconds, reaction pressure is 0.03 MPa, CO gas II and bismuth nitrite
- the result is a utilization rate of NO of 99.3%
- Example 2 According to the procedure of Example 1, except that the molar ratio of CO gas II to CO gas I is 80:1; the weight composition of the catalyst I is 0.8% Pd + 10% Ce + 0.003% Zr + 0.507% Fe/TiO 2 The weight composition of the catalyst II was 0.6% Pd + 0.2% Cu + 0.08% Fe/a-Al 2 O 3 .
- the C 2 ⁇ C 4 alkanol is selected from the group consisting of ethanol.
- the operating conditions of the rotating bed supergravity reactor I are: reaction temperature 30 ° C, reaction pressure 1.0 MPa, reaction contact time 50 sec, NO with ethanol and oxygen
- the molar ratio is 1:8: 0.25
- the operating conditions of the rotating bed supergravity reactor II are: reaction temperature is 45 ° C, reaction pressure is 0.01 MPa, reaction contact time is 0.8 seconds, NO in NO-containing gas phase stream V
- the molar ratio to sterol and oxygen is 1:6:0.22
- the operating conditions of the coupled reactor I are: reaction temperature is 160 ° C, reaction contact time is 120 seconds, reaction pressure is 0.01 MPa, CO gas I and nitrous acid
- the molar ratio of ethyl ester is 12:1
- the reaction conditions of coupling reactor II are: reaction temperature is 125 ° C, reaction contact time is 3 seconds, reaction pressure is 0.03 MPa, CO gas II and decyl nitrite effluent
- the molar ratio of VII is 1.3:1
- Example 2 According to the procedure of Example 1, except that the molar ratio of CO gas II to CO gas I is 60:1; the weight composition of catalyst I is 0.11% Pd + 0.6% Ba + 0.2% Fe / magnesium oxide, and the weight composition of catalyst II is 0.34. % Pd + 1.0% K + 0.46% Mn / a - Al 2 O 3 .
- the C 2 ⁇ C 4 alkanol is selected from the group consisting of ethanol.
- the operating conditions of the rotating bed supergravity reactor I are: reaction temperature 25 ° C, reaction pressure 0.2 MPa, reaction contact time 15 seconds, NO with ethanol and oxygen
- the molar ratio is 1:6:0.26
- the operating conditions of the rotating bed supergravity reactor II are: the reaction temperature is 55 ° C, the reaction pressure is 0.05 MPa, the reaction contact time is 2.5 seconds, and the NO in the NO-containing gas phase stream V
- the molar ratio to sterol and oxygen is 1:4: 0.18
- the operating conditions of coupling reactor I are: reaction temperature is 100, reaction contact time is 4 seconds, reaction pressure is 0.01 MPa, CO gas I and ethyl nitrite
- the molar ratio is 4:1
- the reaction conditions of the coupling reactor II are: reaction temperature is 135 ° C, reaction contact time is 2 seconds, reaction pressure is 0.03 MPa, CO gas II and methyl nitrite effluent VII
- the molar ratio is 1.4:1, the result is 98.9% utilization
- Example 2 According to the procedure of Example 1, except that the molar ratio of CO gas II to CO gas I is 120:1; the weight composition of catalyst I is 0.32% Pd + 0.25% Fe/aA 1 2 0 3 , and the weight composition of catalyst II is 0.34%. Pd + 1.0% K + 0.46% Mn / a - Al 2 O 3 .
- the C 2 ⁇ C 4 alkanol is selected from n-butanol.
- reaction temperature is 65 ° C
- reaction pressure is 0.8 MPa
- reaction contact time is 100 seconds
- the molar ratio of butanol to oxygen is 1:12: 0.24
- the operating conditions of the rotating bed supergravity reactor II are: reaction temperature is 48 ° C, reaction pressure is O.
- reaction contact time is 12 seconds, containing NO gas phase
- the molar ratio of NO to sterol and oxygen in stream V is 1:8: 0.24;
- the operating conditions of coupling reactor I are: reaction temperature is 140 ° C, reaction contact time is 80 seconds, reaction pressure is 0.2 MPa, CO
- the molar ratio of gas I to butyl nitrite is 10:1;
- the reaction conditions of coupling reactor II are: reaction temperature is 145 ° C, reaction contact time is 5 seconds, reaction pressure is 0.03 MPa, CO gas II and sub
- the molar ratio of cerium nitrate effluent VII is 1.2:1, and the result is
- the utilization rate of NO was 99.2%, the content of nitrogen oxides in the vent gas was 5 ppm, the space time yield of dinonyl oxalate was 1041 g/(hr. liter), and the selectivity of dinonyl oxalate was 98.7%.
- Example 2 According to the procedure of Example 1, except that the molar ratio of CO gas II to CO gas I is 10:1; the weight composition of catalyst I is 0.41% Pd + 0.82% Fe/a-Al 2 O 3 , and the weight composition of catalyst II is 0.22. % Pd + 1.0% Mg + 2.10% Mn / a - Al 2 O 3 .
- the C 2 ⁇ C 4 alkanol is selected from n-propanol.
- the operating conditions in the rotating bed supergravity reactor I are: reaction temperature is 48 ° C, reaction pressure is 1.8 MPa, reaction contact time is 45 seconds, NO and positive
- the molar ratio of propanol to oxygen is 1:30: 0.23
- the operating conditions of the rotating bed supergravity reactor II are: reaction temperature is 45 ° C, reaction pressure is O.OlMPa, reaction contact time is 3 seconds, NO-containing gas phase stream
- the molar ratio of NO to methanol and oxygen in V is 1:3: 0.20
- the operating conditions of coupling reactor I are: reaction temperature is 150 ° C, reaction contact time is 3 seconds, reaction pressure is 0.05 MPa, CO gas
- the molar ratio of I to propyl nitrite is 5:1
- the reaction conditions of coupling reactor II are: reaction temperature is 148 ° C, reaction contact time is 6 seconds, reaction pressure is 0.05 MPa, CO gas II and nitrous acid
- Example 2 According to the procedure of Example 1, except that the molar ratio of CO gas II to CO gas I is 10:1; the weight composition of catalyst I is 0.12% Pd + 0.33% Fe/a-Al 2 O 3 , and the weight composition of the catalyst is 0.52. % Pd + 1.5% Mg + 2.30% Mn / a - Al 2 O 3 .
- the C 2 ⁇ C 4 alkanol is selected from n-butanol.
- the operating conditions in the rotating bed supergravity reactor I are: reaction temperature is 53 ° C, reaction pressure is 0.2 MPa, reaction contact time is 18 seconds, NO and positive
- the molar ratio of butanol to oxygen is 1:5:0.20
- the operating conditions of the rotating bed supergravity reactor II are: reaction temperature is 50 ° C, reaction pressure is O.OlMPa, reaction contact time is 4 seconds, and NO-containing gas phase stream
- the molar ratio of NO to sterol and oxygen in V is 1:8:0.20
- the operating conditions of coupling reactor I are: reaction temperature is 95 ° C, reaction contact time is 10 seconds, reaction pressure is 0.4 MPa, CO gas
- the molar ratio of I to butyl nitrite is 15:1
- the reaction conditions of coupling reactor II are: reaction temperature is 120 ° C, reaction contact time is 4.5 seconds, reaction pressure is 0.05 MPa, CO gas II and nitrous acid
- the molar ratio of the oxime ester effluent VII
- Example 1 According to the procedure of Example 1, only the NO gas is a mixed gas having a volume fraction of NO of 95% and a volume fraction of nitrogen of 5%, and the nitrogen balance of the inlet and outlet systems, without the rotating bed supergravity reactor I and the coupling reactor I, NO The gas was directly replenished and mixed with the NO-containing gas phase effluent IX, and the catalyst II had a weight composition of 0.52% Pd++2.0% Mn/a-Al 2 O 3 .
- the operating conditions of the rotating bed supergravity reactor II are: the reaction temperature is 50 ° C, the reaction pressure is O.OlMPa, the reaction contact time is 4 seconds, and the molar ratio of NO to the sterol and oxygen in the NO-containing vapor phase V is 1 : 7 : 0.25;
- the reaction conditions of the coupling reactor II are: the reaction temperature is 122 ° C, the reaction contact time is 6 seconds, the reaction pressure is 0.05 MPa, and the molar ratio of the CO gas II to the decyl nitrite effluent VII is Under the condition of 1.2:1, the result is 99.0% of NO, the content of nitrogen oxides in venting tail gas is 0.7%, and the space-time yield of dimethyl oxalate is 960g/(h.L), dimethyl oxalate The selectivity of the ester was 98.1%.
- Example 1 According to the procedure of Example 1, only the NO gas is a mixed gas having a volume fraction of NO of 90% and a volume fraction of nitrogen of 10%, and the nitrogen balance of the inlet and outlet systems, without the rotating bed supergravity reactor I and the coupling reactor I, NO The mixed gas was directly supplied and mixed with the NO-containing gas phase effluent IX, and the catalyst II had a weight composition of 0.32% Pd++2.0%Fe/a-A1 2 0 3 .
- the operating conditions of the rotating bed supergravity reactor II are: the reaction temperature is 40 ° C, the reaction pressure is 0.02 MPa, the reaction contact time is 2 seconds, and the molar ratio of NO to the sterol and oxygen in the NO-containing gas phase V is 1: 8 : 0.25;
- the reaction conditions of the coupled reactor II are: the reaction temperature is 130 ° C, the reaction contact time is 6 seconds, the reaction pressure is 0.05 MPa, and the molar ratio of the CO gas II to the methyl nitrite effluent VII is 1.4. Under the condition of 1, the result is 98.5% of NO, the content of nitrogen oxides in the exhaust gas is 0.6%, and the space-time yield of dinonyl oxalate is 990 g / (hr. liter), dinonyl oxalate The selectivity was 99.0%. [Comparative Example 1]
- Example 6 According to the same catalyst, conditions and reaction raw materials of Example 6, except that the C 2 ⁇ C 4 alkanol was substituted with decyl alcohol, the result was: the utilization rate of NO was 90.0%, and the nitrogen oxides in the exhaust gas were vented. The content was 1%, the space time yield of dimethyl oxalate was 880 g / (hr. liter), and the selectivity of dimethyl oxalate was 95.4%.
- nebulizer and reaction raw materials of Example 6 only the rotating bed supergravity reactor I and the rotating bed supergravity reactor II were both fixed gravity reactors, and the results were as follows: the utilization rate of NO was 89.3%. The content of nitrogen oxides in the vent gas was 0.9%, the space time yield of dinonyl oxalate was 870 g/(hr. liter), and the selectivity of dinonyl oxalate was 94.1%.
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AU2011240710A AU2011240710B2 (en) | 2010-04-15 | 2011-04-13 | Method for preparing oxalate from carbon monoxide by gaseous phase method |
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CN102580435A (zh) * | 2012-01-19 | 2012-07-18 | 安徽淮化股份有限公司 | 气液分离器及其在分离草酸二甲酯中的应用 |
JP2013533225A (ja) * | 2010-06-11 | 2013-08-22 | 中国石油化工股▲ふん▼有限公司 | Co気相法を用いたシュウ酸塩の製造方法 |
US9776950B2 (en) | 2014-07-04 | 2017-10-03 | Ube Industries, Ltd. | Ester production method and ester production device |
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CN103664594B (zh) * | 2012-09-26 | 2015-06-10 | 中国石油化工股份有限公司 | 气相法co偶联制备草酸二甲酯的运行控制方法 |
CN104557536B (zh) * | 2013-10-24 | 2016-03-30 | 中国石油化工股份有限公司 | 一种丁二酸单甲酯的制备方法 |
RU2702116C1 (ru) * | 2018-10-22 | 2019-10-04 | Пуцзин Кемикал Индастри Ко., Лтд | Катализатор синтеза оксалата посредством реакции связывания co, способ его получения и его применения |
AU2018447125B2 (en) * | 2018-10-22 | 2022-11-24 | Pujing Chemical Industry Co., Ltd | Carbonylation catalyst and preparation thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4629806A (en) * | 1981-01-23 | 1986-12-16 | Union Carbide Corporation | Vapor state formation of diesters of oxalic acid |
CN101993366A (zh) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | 由co气相法制备草酸酯的方法 |
Family Cites Families (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2811181A1 (de) * | 1978-03-15 | 1979-09-20 | Hoechst Ag | Verfahren zur herstellung von distickstoffmonoxid |
AU545415B2 (en) * | 1980-08-26 | 1985-07-11 | Ube Industries, Ltd. | Oxalic esters from carbon monoxide and nitrous acid ester |
JPS57122042A (en) * | 1981-01-23 | 1982-07-29 | Ube Ind Ltd | Preparation of oxalic acid diester |
SU1298188A1 (ru) * | 1985-01-04 | 1987-03-23 | Предприятие П/Я В-2281 | Способ получени окиси азота |
US4908466A (en) * | 1987-09-29 | 1990-03-13 | Union Carbide Chemicals And Plastics Company Inc. | Process and reaction vessel for production of alkyl nitrite |
CH678172A5 (zh) | 1989-06-07 | 1991-08-15 | Zellweger Uster Ag | |
JP3804818B2 (ja) * | 1998-03-31 | 2006-08-02 | 宇部興産株式会社 | シュウ酸ジアルキルの製造法 |
JP4214858B2 (ja) * | 2002-08-13 | 2009-01-28 | 宇部興産株式会社 | シュウ酸ジアルキルの製法 |
JP4304446B2 (ja) * | 2002-08-30 | 2009-07-29 | 宇部興産株式会社 | シュウ酸ジアルキルの製造法 |
US7288664B2 (en) * | 2004-03-30 | 2007-10-30 | Bela Kleiner | Reverse Kleiner method for manufacturing nitrogen dioxide, nitric oxide, nitric acid, metallic ascorbates and alkyl ascorbates of vitamin C |
CN100513304C (zh) | 2005-09-30 | 2009-07-15 | 通辽金煤化工有限公司 | 一种合成草酸酯用的亚硝酸酯气体的生产方法 |
CN101143821B (zh) * | 2007-10-23 | 2010-08-11 | 天津大学 | Co偶联制备草酸二乙酯的方法 |
CN101492370B (zh) * | 2008-12-18 | 2012-07-25 | 中国石油化工股份有限公司 | Co偶联制草酸酯的方法 |
RU2564028C2 (ru) * | 2010-04-15 | 2015-09-27 | Чайна Петролеум & Кемикал Корпорейшн | Способ производства с1-с4 алкилнитрита |
CN102219698B (zh) * | 2010-04-15 | 2014-04-23 | 中国石油化工股份有限公司 | 生产c1~c4烷基亚硝酸酯的方法 |
-
2010
- 2010-04-15 CN CN2010101469992A patent/CN102219680B/zh active Active
-
2011
- 2011-04-13 US US13/641,457 patent/US8871968B2/en active Active
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- 2011-04-13 WO PCT/CN2011/000649 patent/WO2011127752A1/zh active Application Filing
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4629806A (en) * | 1981-01-23 | 1986-12-16 | Union Carbide Corporation | Vapor state formation of diesters of oxalic acid |
CN101993366A (zh) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | 由co气相法制备草酸酯的方法 |
Non-Patent Citations (1)
Title |
---|
WANG BAOWEI ET AL.: "Optimization of Cyclical Process for CO Coupling Regeneration", COMPUTER AND CHEMICAL ENGINEERING, vol. 24, 2000, pages 1337 - 1341, XP026981839 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2013533225A (ja) * | 2010-06-11 | 2013-08-22 | 中国石油化工股▲ふん▼有限公司 | Co気相法を用いたシュウ酸塩の製造方法 |
CN102580435A (zh) * | 2012-01-19 | 2012-07-18 | 安徽淮化股份有限公司 | 气液分离器及其在分离草酸二甲酯中的应用 |
US9776950B2 (en) | 2014-07-04 | 2017-10-03 | Ube Industries, Ltd. | Ester production method and ester production device |
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