CN102008922A - Process method and method for regenerating methyl nitrite in production of dimethyl oxalate - Google Patents
Process method and method for regenerating methyl nitrite in production of dimethyl oxalate Download PDFInfo
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Abstract
The invention belongs to the technical field of the production of dimethyl oxalate, and particularly relates to a process method and a device for regenerating methyl nitrite in the production of the dimethyl oxalate. In the method, the utilization rate of nitric oxide in the regenerative process is improved, and the using amount of methanol is reduced. The device comprises a rotary filler bed, wherein a gas inlet of the rotary filler bed is connected with sources of nitrogen, oxygen and nitric oxide respectively, a liquid inlet is connected with a methanol storage tank, a liquid outlet is connected with an inlet of a methanol-water mixture storage tank, and a gas outlet is connected with a condenser I. The process method comprises the following steps of: opening the rotary filler bed, so that the nitric oxide, the nitrogen and the oxygen are contacted and reacted with absolute methanol in the rotary filler bed to form a gas phase and a liquid phase; and discharging the gas phase, condensing, and allowing the liquid phase to flow into the methanol-water mixture storage tank. The process method has the advantages that: the process reaction efficiency is high; all NO is used efficiently; and the equipment has a compact structure and small volume and requires a small investment. The equipment has the advantages of making operation easy, along with simple structure, small energy consumption, simple flow, convenience for starting and stopping and the like.
Description
Technical field
The invention belongs to the technical field that dimethyl oxalate is produced, be specifically related to the process and the device of methyl nitrite regeneration in a kind of dimethyl oxalate production process, particularly nitric oxide production recycling.
Background technology
Dimethyl 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 dimethyl 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 preparing ethylene glycol by using dimethyl oxalate plus hydrogen, 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.
Shortcomings such as the production route of present traditional dimethyl oxalate is to utilize oxalic acid and methyl alcohol generation esterification to prepare, and there is the cost height in this production technology, and energy consumption is big, and is seriously polluted have certain gap with international most advanced level.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 dimethyl 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 dimethyl 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 dimethyl oxalate to carry out in two steps:
2CO+2CH
3ONO → (COOCH
3)
2+ 2NO (coupling reaction)
2NO+2CH
3OH+0.5O
2→ 2CH
3ONO+H
2O (regenerative response)
2CO+2CH
3OH+0.5O
2→ (COOCH
3)
2+ H
2O (overall reaction)
In regenerative response, NO, O
2At first react the formation methyl nitrite with methyl alcohol, this reaction need not catalyst, and reaction speed is fast, and CO and methyl nitrite carry out carbonylation under catalyst action then, forms dimethyl 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 methyl 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 dimethyl oxalate research, the recycling dimethyl oxalate synthesizer key of running smoothly that become of NO, this problem relate to methyl 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 methyl 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 methyl nitrite generation, has also formed accessory substance nitric acid and formaldehyde.Methyl nitrite be regenerated as four reactions (1)-(4), the summation of these four reactions can obtain the regenerative response of methyl nitrite.
On the one hand, can find out, may produce accessory substance nitric acid and formaldehyde 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 methyl 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 formaldehyde, 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 methanol solution diminishes in the regenerator, can make the side reaction aggravation when methanol quality content is lower than 70%, and the generating rate of methyl nitrite reduces; Methanol aqueous solution also needs to make with extra care with rectifying column simultaneously, even methyl alcohol 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 the methyl alcohol addition can be reduced to about chemical dosage ratio.As n (methyl alcohol)/when n (NO) mol ratio is 0.8-2.2, the methyl nitrite selectivity raises earlier gradually, when mol ratio peaks to 1.5 the time, descends gradually then, illustrate that amount of methanol helps suppressing side reaction, the generation of promotion methyl nitrite.Consider the load of too much methyl alcohol except meeting increase downstream separation operation, the thermic load of methanol gasifying chamber is arranged on also having increased, suitable n (methyl alcohol)/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 dimethyl ester, 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 methyl nitrite regenerative response and process conditions need satisfy in the dimethyl 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 methyl alcohol, 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 formaldehyde 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 methyl alcohol, cause problems such as side reaction increase and rectifying load are big to occur.
The objective of the invention is to overcome the drawback of present production dimethyl oxalate, proposed to improve in the regenerative process utilization rate of NO.
Summary of the invention
The present invention is in order to improve in the dimethyl oxalate production process nitric oxide production utilization rate in the methyl nitrite regenerative process and to reduce the use amount of methyl alcohol.
The present invention adopts following technical scheme to realize:
Be used for the device of dimethyl oxalate production process methyl nitrite regeneration, it is characterized in that comprising rotary packed bed; Rotary packed bed gas feed connects separate nitrogen, oxygen and nitric oxide production source pipeline respectively, liquid-inlet is connected with the methyl alcohol 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 methyl alcohol storage tank through condenser II, and rotary packed bed gas vent connects 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 process of methyl nitrite regeneration in the dimethyl oxalate production process, in the above-mentioned device that is used for the regeneration of dimethyl oxalate production process methyl nitrite, finish, its step is as follows, open rotary packed bed, regulate rotating speed, nitric oxide, nitrogen and oxygen are introduced rotary packed bed gas feed respectively, nitric oxide and oxygen are introduced in opposite directions, absolute methanol is introduced rotary packed bed liquid-inlet, enter packing layer and absolute methanol after nitric oxide, nitrogen and the oxygen mix and in rotary packed bed, carry out haptoreaction, generate gas phase and liquid phase; Gaseous component comprises methyl nitrite, methyl alcohol and nitrogen, after discharging, rotary packed bed gas vent carries out condensation, the mixture of the first alcohol and water of liquid phase enters the alcohol-water mixture storage tank after the condensation, and the methyl nitrite gas that contains nitrogen of gas phase enters last operation and recycles; Liquid phase component comprises the first alcohol and water, flows into the alcohol-water mixture storage tank from rotary packed bed liquid outlet, enters rectifying column then, carry out pure moisture from, the methyl alcohol after separate purifying is discharged by the gas vent of rectifying column, becomes liquid after condensation, enter the methyl alcohol storage tank, recycle.The volume ratio of nitric oxide, nitrogen and oxygen is 4～6: 2.5～5: 1～1.5.Methyl alcohol and nitric oxide production mol ratio are 1.2～1.8 in rotary packed bed.Rotary packed bed rotor speed is 200-2800r/min, and rotary packed bed interior gas liquid reaction temperature is 30-40 ℃.Temperature is 70～80 ℃ in the rectifying column.
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 formaldehyde, system is unfavorable to entire reaction, causes the NO utilization rate low, finally relate to methyl nitrite regenerative response and with the matching problem of coupling reaction speed.The present invention 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 methyl nitrite with methyl alcohol 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 methyl alcohol.
The present invention has following beneficial effect: described technology is improved rotary packed bed air inlet, 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.And this technology has reaction efficiency height, NO and all realizes advantages such as efficient utilization, apparatus structure compactness, volume are little, small investment.
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 methyl nitrite (abbreviation methyl esters) are little, flow process is simple, the start-stop car makes things convenient for.
Description of drawings
Fig. 1 methyl nitrite regeneration technology flow chart.
Fig. 2 is rotary packed bed structural representation.
Among the figure: the 1-spinner flowmeter, 2-methyl alcohol storage tank, 3-is rotary packed bed, 4-condenser I, 5-contain the methyl 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
A kind of device that is used for the regeneration of dimethyl oxalate production process methyl nitrite is characterized in that comprising rotary packed bed 3; 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 present invention rotary packed bed 3 gas feed 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 methyl alcohol 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 methyl alcohol 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 methyl nitrite regeneration in the dimethyl oxalate production process, in the above-mentioned device that is used for the regeneration of dimethyl oxalate production process methyl 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 methanol is introduced rotary packed bed inlet, nitric oxide, enter packing layer and absolute methanol after nitrogen and the oxygen mix and in rotary packed bed 3, carry out haptoreaction, generate gas phase and liquid phase; Gaseous component comprises methyl nitrite, methyl alcohol and nitrogen, gas vent from rotary packed bed 3 carries out condensation through condenser I 4 after discharging, the mixture of the first alcohol and water of liquid phase enters alcohol-water mixture storage tank 6 after the condensation, and the methyl nitrite gas 5 that contains nitrogen of gas phase enters last operation and recycles (last operation is that methyl nitrite and CO reaction generate dimethyl oxalate and NO); Liquid phase component comprises the first 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 methyl alcohol that separates after purifying is discharged by the rectifying column gas vent, after condenser II 10 condensations, become liquid, enter methyl alcohol 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 methyl alcohol 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 70～80 ℃ in rectifying column, and process rectifying column and condensed methanol quality concentration are greater than 90%.
Embodiment 1:
Handle the methyl 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 methyl alcohol: 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 80 ℃, and methanol concentration is 94% after the rectifying, after gas-liquid is reacted in rotary packed bed, gas vent NO molar fraction is 0.0011, and the selectivity of methyl nitrite is 99.2%.
Embodiment 2:
Handle the methyl 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 methyl alcohol: 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 70 ℃, and methanol concentration is 91% after the rectifying, after gas-liquid is reacted in rotary packed bed, gas vent NO molar fraction is 0.0008, and the selectivity of methyl nitrite is 99.9%.
Embodiment 3:
Handle the methyl 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: 3.77: 1.23, the mol ratio that enters rotary packed bed middle methyl alcohol: 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 75 ℃, and methanol concentration is 93% after the rectifying, after gas-liquid is reacted in rotary packed bed, gas vent NO molar fraction is 0.00025, and the selectivity of methyl nitrite is 99.5%.
Keep the amount of oxygen relative deficiency in the foregoing description, NO and methyl alcohol are all excessive, therefore with methyl nitrite selectivity be index, its yield is expressed as: the selectivity of methyl nitrite=unit interval generates the oxygen amount of substance that oxygen amount of substance * 100%/unit interval that methyl nitrite consumes reacts away.
Claims (10)
1. a device that is used for the regeneration of dimethyl oxalate production process methyl nitrite 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 methyl alcohol 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 methyl alcohol storage tank (2) through condenser II (10), and the gas vent of rotary packed bed (3) connects condenser I (4).
2. the device that is used for the regeneration of dimethyl oxalate production process methyl nitrite 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 that is used for the regeneration of dimethyl oxalate production process methyl nitrite 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 that is used for dimethyl oxalate production process methyl nitrite regeneration according to claim 3 is characterized in that the position that rotary packed bed (3) are provided with three gas feeds is taper.
5. the process of methyl nitrite regeneration in the dimethyl oxalate production process, in the device that is used for dimethyl oxalate production process methyl nitrite regeneration as claimed in claim 1 or 2, finish, it is characterized in that step is as follows: open rotary packed bed (3), regulate rotating speed, with nitric oxide (14), nitrogen (13) and oxygen (12) are introduced rotary packed bed gas feed respectively, nitric oxide (14) and oxygen (12) are introduced in opposite directions, absolute methanol is introduced rotary packed bed liquid-inlet (3.5), nitric oxide, enter packing layer (3.3) after nitrogen and the oxygen mix and in rotary packed bed, carry out haptoreaction, generate gas phase and liquid phase with absolute methanol; Gaseous component comprises methyl nitrite, methyl alcohol and nitrogen, after discharging, rotary packed bed gas vent carries out condensation, the mixture of the first alcohol and water of liquid phase enters alcohol-water mixture storage tank (6) after the condensation, and the methyl nitrite gas (5) that contains nitrogen of gas phase enters last operation and recycles; Liquid phase component comprises the first alcohol and water, flow into alcohol-water mixture storage tank (6) from rotary packed bed liquid outlet (3.2), enter rectifying column (8) then, carry out pure moisture from, the methyl alcohol that separates after purifying is discharged by the gas vent (9) of rectifying column, after condensation, become liquid, enter methyl alcohol storage tank (2), recycle.
6. the process of methyl nitrite regeneration in the dimethyl oxalate production process, in the device that is used for dimethyl oxalate production process methyl nitrite regeneration as claimed in claim 4, finish, it is characterized in that step is as follows: open rotary packed bed (3), regulate rotating speed, with nitric oxide (14), nitrogen (13) and oxygen (12) are introduced rotary packed bed gas feed respectively, nitric oxide (14) and oxygen (12) are introduced in opposite directions, absolute methanol is introduced rotary packed bed liquid-inlet (3.5), nitric oxide, enter packing layer (3.3) after nitrogen and the oxygen mix and in rotary packed bed, carry out haptoreaction, generate gas phase and liquid phase with absolute methanol; Gaseous component comprises methyl nitrite, methyl alcohol and nitrogen, after discharging, rotary packed bed gas vent carries out condensation, the mixture of the first alcohol and water of liquid phase enters alcohol-water mixture storage tank (6) after the condensation, and the methyl nitrite gas (5) that contains nitrogen of gas phase enters last operation and recycles; Liquid phase component comprises the first alcohol and water, flow into alcohol-water mixture storage tank (6) from rotary packed bed liquid outlet (3.2), enter rectifying column (8) then, carry out pure moisture from, the methyl alcohol that separates after purifying is discharged by the gas vent (9) of rectifying column, after condensation, become liquid, enter methyl alcohol storage tank (2), recycle.
7. the process of methyl nitrite regeneration in the dimethyl oxalate production process according to claim 6, the volume ratio that it is characterized in that nitric oxide, nitrogen and oxygen is 4～6: 2.5～5: 1～1.5.
8. the process of methyl nitrite regeneration in the dimethyl oxalate production process according to claim 6, its feature enter rotary packed bed in methyl alcohol and nitric oxide production mol ratio be 1.2～1.8.
9. the process of methyl nitrite regeneration in the dimethyl oxalate production process according to claim 6, its feature is 200-2800r/min in rotary packed bed rotor speed, rotary packed bed interior gas liquid reaction temperature is 30-40 ℃.
10. the process of methyl nitrite regeneration in the dimethyl oxalate production process according to claim 6, its feature temperature in rectifying column is 70～80 ℃.
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| 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 |
| CN102807492A (en) * | 2012-08-30 | 2012-12-05 | 安徽淮化股份有限公司 | Process device for producing methyl nitrite |
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| CN103664594A (en) * | 2012-09-26 | 2014-03-26 | 中国石油化工股份有限公司 | Operational control method for preparing dimethyl oxalate through vapor phase method CO coupling |
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