CN201862400U - Ethyl nitrite regenerating device in production process of diethyl oxalate - Google Patents
Ethyl nitrite regenerating device in production process of diethyl oxalate Download PDFInfo
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- CN201862400U CN201862400U CN2010205339438U CN201020533943U CN201862400U CN 201862400 U CN201862400 U CN 201862400U CN 2010205339438 U CN2010205339438 U CN 2010205339438U CN 201020533943 U CN201020533943 U CN 201020533943U CN 201862400 U CN201862400 U CN 201862400U
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- nitric oxide
- ethyl nitrite
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Abstract
The utility model belongs to the technical field of diethyl oxalate production, and particularly relates to an ethyl nitrite regenerating device in the production process of diethyl oxalate, which increases the utilization ratio of nitric oxide and reduces the use amount of ethanol in the regeneration process. The ethyl nitrite regenerating device in the production process of the diethyl oxalate comprises a rotating packed bed, wherein a gas inlet of the rotating packed bed is respectively connected with mutually independent source pipelines of nitrogen, oxygen and nitric oxide, a liquid inlet is connected with an ethanol storage tank, a liquid outlet is connected with an inlet of an alcohol and water mixture storage tank, an outlet of the alcohol and water mixture storage tank is connected with an inlet of a rectifying tower, a gas outlet of the rectifying tower is connected with the ethanol storage tank through a condenser II, and a gas outlet of the rotating packed bed is connected with a condenser I. The device has the advantages of simple structure, small energy consumption, simple process and convenience of start and stop, and is easy to operate; and the realized process has high reaction efficiency, the nitric oxide is fully efficiently utilized, and the device has a compact structure, a small size and less investment.
Description
Technical field
The utility model belongs to the technical field that diethy-aceto oxalate is produced, and is specifically related to the device of nitrous ether (ethyl nitrite) regeneration in a kind of diethy-aceto oxalate production process.
Background technology
Diethy-aceto oxalate is important Organic Chemicals and intermediate, is widely used in fine chemistry industry and prepares in the industry such as various dyestuffs, medicine, agricultural chemicals, but also be important solvent and extractant etc.The diethy-aceto oxalate hydrolysis makes oxalic acid and can produce the specialty chemicals of high added value and be used for electronic information and national defence atomic energy industry, ammonification can get organic chemical industry's products such as oxamide, by diethy-aceto oxalate hydrogenation preparing ethylene glycol, ethylene glycol also is important chemical material, be used for synthetic fibers in a large number, in the production of unsaturated polyester resin and plastic sheeting, be used to make the adhesive of fine chemistry industry in addition, solvent, prospects such as plasticizer are very wide, China is ethylene glycol consumption big country, estimate that China's ethylene glycol output in 2010 will reach 4,200,000 tons, and demand when the time comes will reach 7,200,000 tons, output can not satisfy domestic demand far away, need a large amount of imports, ethylene glycol has good development prospect in China.
Sodium formate method and nitric acid oxidation method are adopted in present domestic diethy-aceto oxalate production mostly, and raw materials used cost height is seriously polluted, with international most advanced level certain gap is arranged.External oxalic acid is produced route and is also brought in constant renewal in, last century the seventies mainly based on petrochemical industry, carried out the improvement of raw material route, as French Luo Na-Rhone-Poulenc oxidation of propylene synthesis of oxalic acid, can reach more than 90% in propylene oxalic acid yield.Enter the last century the eighties because crisis once appearred in petroleum-based energy, carried out " carbonizer " the new raw material route that replaces oil with coal in the world again.Carbon monoxide gas phase coupling catalysis system diethy-aceto oxalate wherein, it is the focus of " C1 chemical industry " new technology research at present in the world, it also is one of the important topic of the non-petroleum path sustainable development of China Eleventh Five-Year Plan emphasis project verification, the carbon monoxide raw material sources are extensive and inexpensive, can produce from coal or natural gas, special energy resource structure for the oil-poor weak breath of the rich coal of China, with carbon monoxide system diethy-aceto oxalate is most economical rational route, has opened up a new way utilizing the coal resources synthesizing glycol.
Carbon monoxide gas-phase catalytic coupling prepares the course of reaction of diethy-aceto oxalate to carry out in two steps:
2CO+2C
2H
5ONO → (COOC
2H
5)
2+ 2NO (coupling reaction)
2NO+2C
2H
5OH+0.5O
2→ 2C
2H
5ONO+H
2O (regenerative response)
2CO+2C
2H
5OH+0.5O
2→ (COOC
2H
5)
2+ H
2O (overall reaction)
In regenerative response, NO, O
2At first react the formation nitrous ether (ethyl nitrite) with ethanol, this reaction need not catalyst, and reaction speed is fast, and CO and nitrous ether (ethyl nitrite) carry out carbonylation under catalyst action then, forms diethy-aceto oxalate and NO, and NO is recycled to and realizes in the regenerative response recycling.
This technical process, from technology with consider economically must be in addition recycling with accessory substance NO that coupling reaction produced, so the reaction of NO regeneration nitrous ether (ethyl nitrite) has also caused great concern.In fact can CO catalytic coupling process carry out smoothly, depends primarily on the degree of regenerative response coupling, has only when two reaction rates of catalytic coupling and regeneration are complementary, and just can reach coupling-regeneration cycle and form free of contamination self-enclosed system.This step is the key that whole technical process reaches.
Along with scientific worker's going deep into to diethy-aceto oxalate research, the recycling diethy-aceto oxalate synthesizer key of running smoothly that become of NO, this problem relate to nitrous ether (ethyl nitrite) regenerative response and with the matching problem of coupling reaction speed, analyze the recycling problem of NO, at first the serial reaction that may relate to from the regenerative response of nitrous ether (ethyl nitrite) is set about:
By above-mentioned reaction as seen, process is quite complicated, and successive reaction is arranged, and parallel reaction is arranged, and except that producing the nitrous ether (ethyl nitrite) generation, has also formed accessory substance nitric acid and acetaldehyde.Nitrous ether (ethyl nitrite) be regenerated as four reactions (1)-(4), the summation of these four reactions can obtain the regenerative response of nitrous ether (ethyl nitrite).
On the one hand, can find out, may produce accessory substance nitric acid and acetaldehyde in the reaction from reaction (5)-(10), unfavorable to whole system, so should avoid N in the reaction as far as possible
2O
4Generation, so NO and O
2Can not before reaction, mix, if but in conventional tower equipment, react, because the time of staying of fluid in tower is longer, and fluid skewness in tower, just may cause N
2O
4Generation, therefore need seek to mix and high efficiency reactor that the time of staying is short imperative.NO has inhibitory action to the coupling reaction rate in the coupling reaction simultaneously, and this point requires the content of NO in synthesis gas low as far as possible again, so NO is to NO
2The ratio height of should trying one's best, and NO and O in the nitrous ether (ethyl nitrite) regenerative response
2Stoichiometric proportion be 4: 1, so require NO and O
2Stoichiometric proportion be less than 4: 1; On the other hand, coupling reaction needs to carry out in reducing atmosphere, feed oxygen in the regenerator must be in regenerator total overall reaction, otherwise enter coupler reactor catalyst oxidation will be lost activity with unstripped gas.So select NO and O
2Stoichiometric proportion be greater than 4: 1, make in the exit gas of regenerator oxygen content near zero, therefore, NO and O
2Stoichiometry be compared to the effective recycling of NO and seem particularly important.
In addition, according to reaction (6), pressure is high more in the regenerator, N
2O
4Generate manyly more, in order to reduce product nitric acid and acetaldehyde, pressure is low more good more in the regenerator, adopts normal pressure to react usually for this reason.In order to improve the utilization rate of NO, will analyze from the mechanism of above-mentioned reaction: the speed that nitrogen dioxide is converted into nitrogen tetraoxide increases along with the reduction of temperature, and therefore in order to prevent the generation of nitrogen tetraoxide, temperature can not be too low; The water that regenerative response generates can make that the concentration of ethanolic solution diminishes in the regenerator, can make the side reaction aggravation when the ethanol mass content is lower than 70%, and the generating rate of nitrous ether (ethyl nitrite) reduces; Ethanol water also needs to make with extra care with rectifying column simultaneously, even ethanol can all be recycled, the energy of this section operation consumption also can not look down upon.Therefore,, these a series of problems will be alleviated effectively, and be made this process become real Atom economy course of reaction if amount of alcohol added can be reduced to about chemical dosage ratio.As n (ethanol)/when n (NO) mol ratio is 0.8-2.2, the nitrous ether (ethyl nitrite) selectivity raises earlier gradually, when mol ratio peaks to 1.5 the time, descends gradually then, illustrate that adequate amount of ethanol helps suppressing side reaction, the generation of promotion nitrous ether (ethyl nitrite).Consider the load of too much ethanol except meeting increase downstream separation operation, the thermic load of ethanol vaporizer is arranged on also having increased, suitable n (ethanol)/n (NO) mol ratio should be at 1.5-2, and ratio is near stoichiometric proportion.As carrier gas and protection gas, its content has significant effects to the carrying out and the removing of reaction heat of reaction to nitrogen in system.Generally, nitrogen gas concn is not obvious to the selectivity influence of nitrous acid diethylester, takes all factors into consideration the addition of reactor, and selecting nitrogen gas concn is between the 10-30%.
In sum, the requirement that the consersion unit of nitrous ether (ethyl nitrite) regenerative response and process conditions need satisfy in the diethy-aceto oxalate production process: fluid time of staying in reclaim equiment is short, satisfies NO and O
2Even mixing, fast reaction, reaction efficiency height, improved the utilization rate of NO, stoped the generation of side reaction.Ratio between control temperature and the reactant effectively prevents N
2O
4Generation, simultaneously high efficiency reactor has been avoided using a large amount of ethanol, has reduced the rectifying load, has reduced the generation of side reaction simultaneously.
Usually in bubble tower and packed tower, carry out and above-mentioned regenerative response takes place at present, use these equipment to have following problem:, cause N because fluid time of staying in these equipment is long and mix inequality
2O
4, accessory substance such as nitric acid and acetaldehyde generation, cause the utilization rate of NO lower, thereby the system that makes need add a certain amount of NO in coupling reaction, directly have influence on the proportion relation between the material in coupling and the regenerative response, and mass transfer and reaction efficiency are low in the conventional tower equipment, make to need a large amount of ethanol, cause problems such as side reaction increase and rectifying load are big to occur.
The purpose of this utility model is the drawback that overcomes present production diethy-aceto oxalate, has proposed to improve in the regenerative process utilization rate of NO.
Summary of the invention
The utility model provides the device of nitrous ether (ethyl nitrite) regeneration in a kind of diethy-aceto oxalate production process in order to improve in the diethy-aceto oxalate production process nitric oxide production utilization rate in the nitrous ether (ethyl nitrite) regenerative process and to reduce the use amount of ethanol.
The utility model adopts following technical scheme to realize:
The device of nitrous ether (ethyl nitrite) regeneration is characterized in that comprising rotary packed bed in the diethy-aceto oxalate production process; Rotary packed bed gas feed connects separate nitrogen, oxygen and nitric oxide production source pipeline respectively, liquid-inlet is connected with the ethanol storage tank, liquid outlet links to each other with the import of alcohol-water mixture storage tank, the outlet of alcohol-water mixture storage tank connects the import of rectifying column, the gas vent of rectifying column connects the ethanol storage tank through the condenser II, and rotary packed bed gas vent connects the condenser I.
Rotary packed bed gas feed is provided with three, comprise nitrogen inlet, oxygen inlet and nitric oxide import, oxygen inlet and nitric oxide import are provided with in opposite directions, nitrogen inlet be arranged between oxygen inlet and the nitric oxide import and direction perpendicular to the direction of oxygen inlet and nitric oxide import.Rotary packed bed liquid-inlet and gas vent are tubulose, and gas vent is placed in outside the liquid-inlet.The rotary packed bed position that three gas feeds are set is taper.
The NO that mainly has its source in that the NO cyclic utilization rate is not high in the conventional regeneration system makes NO be oxidized to NO owing to long in the time of staying
2, cause N
2O
4Generation, cause having participated in the part side reaction and cause reaction to generate nitric acid and acetaldehyde, system is unfavorable to entire reaction, causes the NO utilization rate low, finally relate to nitrous ether (ethyl nitrite) regenerative response and with the matching problem of coupling reaction speed.The utility model utilizes the short and high characteristic of mass-transfer efficiency of the rotary packed bed time of staying by theory analysis, suppresses the generation of NO side reaction, and NO and oxygen generate NO
2, just generated N with NO immediately
2O
3, generated nitrous ether (ethyl nitrite) with ethanol thereupon, by appropriate design gas component, system temperature and pressure, its NO is fully reacted, the NO of gas vent and O
2Concentration be bordering on zero, thereby reach the efficient circulation utilization of NO.Compare with the distillation column reactor device with bubble tower, under the prerequisite that reaches the equivalent responses result, greatly reduce the addition of ethanol.
The utlity model has following beneficial effect: rotary packed bed air inlet is improved, make nitric oxide and oxygen finish initial evenly distribution at rotary packed bed air inlet, improved its mixed effect, and it is this is rotary packed bed as reaction unit, in conjunction with the rotary packed bed characteristics and the characteristics of this regenerative response, NO is realized efficient the utilization, make the concentration of oxygen in the final gaseous component and NO almost nil, thereby realized the efficient circulation utilization of NO.Described equipment, simple in structure, easy to operate, compared with prior art, NO utilization rate height, advantages such as the reaction, the energy consumption that efficiently solve NO regeneration nitrous ether (ethyl nitrite) (abbreviation ethyl ester) are little, flow process is simple, the start-stop car makes things convenient for.The technology that realizes by this equipment has reaction efficiency height, NO and all realizes advantages such as efficient utilization, apparatus structure compactness, volume are little, small investment.
Description of drawings
Fig. 1 schematic diagram of the present utility model.
Fig. 2 is rotary packed bed structural representation
Among the figure: the 1-spinner flowmeter, 2-ethanol storage tank, 3-is rotary packed bed, 4-condenser I, 5-contains the nitrous ether (ethyl nitrite) gas of nitrogen, 6-alcohol-water mixture storage tank, 7-liquid pump I, the 8-rectifying column, the gas vent of 9-rectifying column, 10-condenser II, 11-liquid pump II, 12-oxygen, 13-nitrogen, 14-nitric oxide;
3.1-motor, 3.2-liquid outlet, 3.3-packing layer, 3.4-liquid distribution trough, 3.5-liquid-inlet, 3.6-gas vent, 3.7-nitrogen inlet, the import of 3.8-nitric oxide, 3.9-oxygen inlet, 3.10-shell.
The specific embodiment
The device of nitrous ether (ethyl nitrite) regeneration is characterized in that comprising rotary packed bed 3 in a kind of diethy-aceto oxalate production process; Rotary packed bed 3 universal architecture comprises the ring packing layer 3.3 in shell 3.10 and the shell 3.10, gas feed, liquid-inlet 3.5, gas vent 3.6, liquid outlet 3.2 are set on the shell 3.10, packing layer connects rotor, and the middle vacancy of ring packing layer is provided with the liquid distribution trough 3.4 that is connected with liquid-inlet 3.5.The gas feed of the utility model rotary packed bed 3 connects the source pipeline of separate nitrogen 13, oxygen 12 and nitric oxide 14 respectively, and the rotary packed bed position that three gas feeds are set is taper.Gas feed is provided with three, comprise nitrogen inlet 3.7, oxygen inlet 3.9 and nitric oxide import 3.8 are connected with separately gas source pipeline respectively, oxygen inlet 3.9 and nitric oxide import 3.8 are provided with in opposite directions, nitrogen inlet 3.7 is arranged between oxygen inlet 3.9 and the nitric oxide import 3.8, and direction is perpendicular to the direction of oxygen inlet and nitric oxide import, oxygen and two strands of gases of nitric oxide clash and enter rotary packed bed gas feed simultaneously, finish oxygen and nitric oxide production initial evenly distribute, and nitrogen and this two strands of gases are an angle of 90 degrees degree and enter rotary packed bed.Rotary packed bed liquid-inlet 3.5 is connected with ethanol storage tank 2 by liquid pump II 11, liquid outlet 3.2 links to each other with the import of alcohol-water mixture storage tank 6, the outlet of alcohol-water mixture storage tank 6 connects the import of rectifying column 8 by liquid pump I 7, the gas vent 9 of rectifying column connects condenser I 4 through the gas vent that condenser II 10 connects ethanol storage tank 2, rotary packed bed 3.Rotary packed bed liquid-inlet 3.5 and gas vent 3.6 are tubulose, and gas vent 3.6 is placed in outside the liquid-inlet 3.5.
The process of nitrous ether (ethyl nitrite) regeneration in the diethy-aceto oxalate production process, in the above-mentioned device that is used for the regeneration of diethy-aceto oxalate production process nitrous ether (ethyl nitrite), finish, its step is as follows: open rotary packed bed 3, regulate rotor speed, nitric oxide 14 through spinner flowmeter 1 metering, nitrogen 13 and oxygen 12 are introduced rotary packed bed gas feed 3.8 respectively, 3.7 and 3.9, nitric oxide and oxygen are introduced in opposite directions to clash into and are finished initial evenly mixing, three strands of gases mix in bell, absolute ethyl alcohol is introduced rotary packed bed inlet, nitric oxide, enter packing layer and absolute ethyl alcohol after nitrogen and the oxygen mix and in rotary packed bed 3, carry out haptoreaction, generate gas phase and liquid phase; Gaseous component comprises nitrous ether (ethyl nitrite), ethanol and nitrogen, gas vent from rotary packed bed 3 carries out condensation through condenser I 4 after discharging, the mixture of the second alcohol and water of liquid phase enters alcohol-water mixture storage tank 6 after the condensation, and the nitrous ether (ethyl nitrite) gas 5 that contains nitrogen of gas phase enters last operation and recycles (last operation is that nitrous ether (ethyl nitrite) and CO reaction generate diethy-aceto oxalate and NO); Liquid phase component comprises the second alcohol and water, flow into alcohol-water mixture storage tank 6 from rotary packed bed liquid outlet, under the effect of liquid pump I 7, enter rectifying column 8 then, carry out pure moisture from, the ethanol that separates after purifying is discharged by the rectifying column gas vent, after 10 condensations of condenser II, become liquid, enter ethanol storage tank 2, recycle.The volume ratio of nitric oxide, nitrogen and oxygen is 4～6: 2.5～5: 1～1.5.Entering rotary packed bed middle ethanol and nitric oxide production mol ratio is 1.2～1.8.Rotary packed bed rotor speed is 200-2800r/min, and rotary packed bed interior gas liquid reaction temperature is 30-40 ℃.Temperature is 85～95 ℃ in rectifying column, and process rectifying column and condensed ethanol mass concentration are greater than 90%.
Embodiment 1:
Handle the nitrous ether (ethyl nitrite) regenerative process in certain chemical plant: nitric oxide, nitrogen and oxygen mixed gas tolerance are 50000m
3/ h, the molar fraction ratio of each component is 4: 5: 1, the mol ratio that enters rotary packed bed middle ethanol: NO is 1.2, and rotary packed bed rotating speed is 200r/min, and filler is the stainless steel cloth filler, the temperature of gas-liquid in rotary packed bed is 30 ℃, the temperature of rectifying column is 95 ℃, and concentration of alcohol is 94% after the rectifying, after gas-liquid is reacted in rotary packed bed, gas vent NO molar fraction is 0.0013, and the selectivity of nitrous ether (ethyl nitrite) is 99.3%.
Embodiment 2:
Handle the nitrous ether (ethyl nitrite) regenerative process in certain chemical plant: nitric oxide, nitrogen and oxygen mixed gas tolerance are 50000m
3/ h, the molar fraction ratio of each component is 6: 2.5: 1.5, the mol ratio that enters rotary packed bed middle ethanol: NO is 1.8, and rotary packed bed rotating speed is 2800r/min, and filler is the plastic silk screen filler, the temperature of gas-liquid in rotary packed bed is 40 ℃, the temperature of rectifying column is 85 ℃, and concentration of alcohol is 90% after the rectifying, after gas-liquid is reacted in rotary packed bed, gas vent NO molar fraction is 0.0010, and the selectivity of nitrous ether (ethyl nitrite) is 99.9%.
Embodiment 3:
Handle the nitrous ether (ethyl nitrite) regenerative process in certain chemical plant: nitric oxide, nitrogen and oxygen mixed gas tolerance are 50000m
3/ h, the molar fraction ratio of each component is 5: 3.76: 1.24, the mol ratio that enters rotary packed bed middle ethanol: NO is 1.3, and rotary packed bed rotating speed is 1800r/min, and filler is the stainless steel cloth filler, the temperature of gas-liquid in rotary packed bed is 35 ℃, the temperature of rectifying column is 90 ℃, and concentration of alcohol is 92% after the rectifying, after gas-liquid is reacted in rotary packed bed, gas vent NO molar fraction is 0.0003, and the selectivity of nitrous ether (ethyl nitrite) is 99.4%.
Keep the amount of oxygen relative deficiency in the foregoing description, NO and ethanol are all excessive, therefore the selectivity with nitrous ether (ethyl nitrite) is an index, and its yield is expressed as: the oxygen amount of substance that oxygen amount of substance * 100%/unit interval that the selectivity of nitrous ether (ethyl nitrite)=unit interval generation nitrous ether (ethyl nitrite) consumes reacts away.
Claims (4)
1. the device of nitrous ether (ethyl nitrite) regeneration in the diethy-aceto oxalate production process is characterized in that comprising rotary packed bed (3); The gas feed of rotary packed bed (3) connects separate nitrogen, oxygen and nitric oxide production source pipeline respectively, liquid-inlet (3.5) is connected with ethanol storage tank (2), liquid outlet (3.2) links to each other with the import of alcohol-water mixture storage tank (6), the outlet of alcohol-water mixture storage tank (6) connects the import of rectifying column (8), the gas vent of rectifying column (9) connects ethanol storage tank (2) through condenser II (10), and the gas vent of rotary packed bed (3) connects condenser I (4).
2. the device of nitrous ether (ethyl nitrite) regeneration in the diethy-aceto oxalate production process according to claim 1, it is characterized in that rotary packed bed gas feed is provided with three, comprise nitrogen inlet (3.7), oxygen inlet (3.9) and nitric oxide import (3.8), oxygen inlet (3.9) and nitric oxide import (3.8) are provided with in opposite directions, nitrogen inlet (3.7) be arranged between oxygen inlet (3.9) and the nitric oxide import (3.8) and direction perpendicular to the direction of oxygen inlet (3.9) and nitric oxide import (3.8).
3. the device of nitrous ether (ethyl nitrite) regeneration in the diethy-aceto oxalate production process according to claim 1 and 2, it is characterized in that rotary packed bed liquid-inlet (3.5) and gas vent (3.6) are tubulose, gas vent (3.6) is placed in outside the liquid-inlet (3.5).
4. the device of nitrous ether (ethyl nitrite) regeneration in the diethy-aceto oxalate production process according to claim 3 is characterized in that the position that rotary packed bed (3) are provided with three gas feeds is taper.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010205339438U CN201862400U (en) | 2010-09-14 | 2010-09-14 | Ethyl nitrite regenerating device in production process of diethyl oxalate |
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|---|---|---|---|
| CN2010205339438U CN201862400U (en) | 2010-09-14 | 2010-09-14 | Ethyl nitrite regenerating device in production process of diethyl oxalate |
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| CN201862400U true CN201862400U (en) | 2011-06-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019164A (en) * | 2010-09-14 | 2011-04-20 | 中北大学 | Ethyl nitrite regeneration technological method and device used in diethyl oxalate production process |
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2010
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019164A (en) * | 2010-09-14 | 2011-04-20 | 中北大学 | Ethyl nitrite regeneration technological method and device used in diethyl oxalate production process |
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|---|---|---|---|
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| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110615 Termination date: 20140914 |
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