CN106518675A - Dimethyl oxalate production method with byproduct (dimethyl carbonate) - Google Patents
Dimethyl oxalate production method with byproduct (dimethyl carbonate) Download PDFInfo
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/08—Purification; Separation; Stabilisation
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Abstract
The invention provides a dimethyl oxalate production method with a byproduct (dimethyl carbonate). The method comprises the following steps: (a) introducing reaction materials containing CO and methyl nitrite into a coupling reactor, and carrying out reactions in the presence of a platinum family metal catalyst to obtain a gas phase material flow containing dimethyl oxalate and dimethyl carbonate; (b) introducing the gas phase material flow containing dimethyl oxalate and dimethyl carbonate into an ester separation tower to contact with a methanol material flow from the top of the ester separation tower and an extracting agent material flow containing oxalic acid from the middle of the ester separation tower in a countercurrent contact mode, obtaining crude methanol from the top of the ester separation tower, and obtaining a mixture containing dimethyl oxalate and dimethyl carbonate from the bottom of the ester separation tower; and (c) introducing the mixture into a dimethyl oxalate refining tower, obtaining a dimethyl carbonate product from the top of the dimethyl oxalate refining tower, and obtaining a dimethyl oxalate product from the bottom of the dimethyl oxalate refining tower; wherein the gas phase material flow containing dimethyl oxalate and dimethyl carbonate is not cooled after being introduced into the ester separation tower.
Description
Technical field
The present invention relates to a kind of production method of dimethyl oxalate., further relates to a kind of production dimethyl oxalate.
And while the method for by-product dimethyl carbonate.
Background technology
Dimethyl oxalate. (DMO) is a kind of important intermediate products, and which can hydrolyze oxalic acid processed,
Preparing ethylene glycol can also be hydrogenated with, has important purposes in chemical industry.The synthesis road of dimethyl oxalate.
Line mainly has two：First route is that the route is deposited synthesizing using methanol and oxalic acid esterification
Big, the serious shortcoming of environmental pollution in waste discharge amount；Another route is by carbon monoxide and nitrous
There is coupling reaction under platinum group catalyst to synthesize in sour methyl ester.As Developing Coal Chemical Industry is fast in recent years
Speed, Article 2 route cause extensive concern as coal ECDC into the intermediate steps of gas preparing ethylene glycol.
In Article 2 route, CO is in loading type Pd/α-Al2O3Under catalyst action, at ambient pressure with Asia
Methyl nitrate coupling reaction generates dimethyl oxalate. and NO, and primary response equation is as follows：
2CO+2CH3ONO→(COOCH3)2+2NO。
In the building-up process, side reaction mainly has：The reaction of CO and methyl nitrite generate NO and
Dimethyl carbonate (C3H6O3), methyl nitrite decomposes generation NO, methyl formate (C2H4O2) and first
Alcohol, CO and NO reactions generate N2And CO2.The chemical equation of above-mentioned side reaction is as follows：
CO+2CH3ONO——→2NO+C3H6O3
4CH3ONO——→4NO+C2H4O2+2CH3OH
2CO+2NO——→N2+2CO2。
At present, in existing process, methanol absorption is typically first adopted, then by methanol, dimethyl carbonate
After separating with dimethyl oxalate., pure dimethyl oxalate. product is obtained.Dimethyl oxalate. is typically purified
Need to through alcohol scrubbing tower, alcohol recovery tower technique completing.The pure dimethyl oxalate. product for obtaining can be with
Directly as product or the raw material as synthesizing glycol.As dimethyl carbonate is present altogether with methanol
Boiling phenomenon, the methanol for obtaining and dimethyl carbonate mixed liquor need to adopt membrance separation or variable-pressure rectification or
The technique of extracting rectifying is separated, and obtains pure dimethyl carbonate product.
The patent application US4453026A of Ube company disclose CO and methyl nitrite or
Nitrous ether (ethyl nitrite) is reacted under platinum-group noble metals catalyst, and product is condensed, isolated
Condensed fluid and fixed gas.A certain amount of methanol or ethanol are added during condensation wherein, to avoid
It is mixed into fixed gas and crystallizes in dimethyl oxalate. or ethyl oxalate.Condensed fluid enters primary rectifying column,
Obtain thick dimethyl oxalate. or ethyl oxalate product.
Patent documentation CN101993367A, CN101993365A, CN101993369A,
In CN101993361A, CN101492370A and CN101381309A, CO and nitrites
Product to obtain gas phase distillation and liquid phase distillation through gas-liquid separation, then will contain oxalic acid
The liquid phase distillate of ester carries out separating-purifying again and obtains oxalate crude product.
Aeration tower and dimethyl oxalate. are added using primary flash in patent documentation CN202643601U
The technological process separation of dimethyl oxalate of rectifying column, due to low-temperature methanol washing in aeration tower, is easily caused
Dimethyl oxalate. is in crystallization inside tower.
Disclose CO and methyl nitrite and platinum-group noble metals in patent documentation CN101462961A
Catalyst contact is reacted, and obtains the product comprising dimethyl oxalate. Yu dimethyl carbonate.By product
Contacted with methanol and condensed in sending into condenser, obtained fixed gas and condensed fluid, contain in condensed fluid
There are dimethyl oxalate., dimethyl carbonate, methyl formate and methanol.Condensed fluid feeding distillation column is carried out
Distillation, tower top obtains the azeotropic mixture of dimethyl carbonate and methanol, and tower reactor is obtained containing dimethyl oxalate.
Material.The method flow process is complicated, and as dimethyl oxalate. has of a relatively high condensation point, easily
Crystallize out in condenser wall, finally block condenser.For preventing dimethyl oxalate. because of Crystallization Plugging
Equipment and pipeline, need to be incubated or heat tracing, high energy consumption；Meanwhile, also affect in equipment and pipeline intercrystalline
The yield of dimethyl oxalate..
Additionally, as described above, the coupling reaction in CO and methyl nitrite prepares dimethyl oxalate.
During often inevitably result from dimethyl carbonate.It is well known that dimethyl carbonate and methanol
There is azeotropism, and methanol gasifying latent heat is big, therefore the particularly dimethyl carbonate of low concentration is from first
Separation process complexity in alcohol, long flow path, high energy consumption.
The patent application CN101190884A of Shanghai Jiaohua Co., Ltd discloses a kind of synthesis of oxalic acid
The method of dimethyl ester by-product dimethyl carbonate, first with substantial amounts of methanol by coupling reaction product
Dimethyl carbonate and dimethyl oxalate. absorb together, recycle dimethyl oxalate. separation of extractive distillation first
Alcohol and dimethyl carbonate, finally separation of dimethyl oxalate and dimethyl carbonate again.Due in absorption process
Methanol usage is big, thus is also required to substantial amounts of dimethyl oxalate. for the carbon in separation of extractive distillation methanol
Dimethyl phthalate, while must steam a large amount of methanol from tower top, high energy consumption during methanol is reclaimed.
East China University of Science patent application CN101381309A discloses dimethyl oxalate. building-up process
The method of middle double-column process separating low concentration dimethyl carbonate, first by methanol, dimethyl carbonate and grass
After dimethyl phthalate is separated, then methanol and dimethyl carbonate are separated using variable-pressure rectification.Methanol and carbonic acid two
In methyl ester separation process, flow process complexity, the problem of high energy consumption are resolved not yet.
In a word, in existing process, for the separation method of dimethyl carbonate, whether variable-pressure rectification,
Or separation of extractive distillation, all there is a problem of that the consumption of methanol is big, thus bring methanol and carbonic acid two
Methyl ester separation process flow process is complicated, the problem of high energy consumption.
The content of the invention
It is an object of the invention to provide a kind of produce dimethyl oxalate. while by-product dimethyl carbonate
Method.The method has technological process simple, and energy consumption is low, while obtaining highly purified dimethyl oxalate.
The characteristics of with by-product dimethyl carbonate, without the need for separately through the separating dimethyl carbonate from methanol.
According to an aspect of the present invention, there is provided a kind of production dimethyl oxalate. by-product dimethyl carbonate
Method, comprise the following steps：
A) reaction mass containing CO and methyl nitrite is passed through in coupler reactor, in platinum family
React in the presence of metallic catalyst, obtain the gaseous state thing containing dimethyl oxalate. and dimethyl carbonate
Stream；
B) gaseous stream containing dimethyl oxalate. and dimethyl carbonate is passed through in ester knockout tower,
With enter from ester separation column containing methanol stream and from ester separate midsection entrance containing oxalic acid two
Methyl ester extractant stream counter current contacting, separates column overhead and obtains crude carbinol, and tower reactor is obtained comprising oxalic acid two
The mixture of methyl ester and dimethyl carbonate；With
C) mixture is passed through in dimethyl oxalate. treating column, tower top obtains dimethyl carbonate product
Product, tower reactor obtain dimethyl oxalate. product；
Wherein, the gaseous stream containing dimethyl oxalate. and dimethyl carbonate be passed through ester knockout tower it
It is front without supercooling.
Wherein, the ester knockout tower refers to that tower reactor obtains the separation of dimethyl oxalate. and dimethyl carbonate
Tower.
Preferably, the gaseous stream containing dimethyl oxalate. and dimethyl carbonate is being passed through ester knockout tower
Tower is washed without alcohol before.Washing tower without alcohol carries out alcohol carrying out washing treatment.
Preferred embodiment of the invention, the ester knockout tower include absorber portion, extraction section and carry
Evaporate section；The stripping section is located between the charging aperture of the gaseous stream and ester knockout tower tower reactor, and is filled
There are column plate or filler；The extraction section is located at the charging aperture of the gaseous stream and the extractant stream
Charging aperture between, and be filled with column plate or filler；The absorber portion is located at the extractant stream
Between charging aperture and the charging aperture containing methanol stream, and column plate or filler are housed.
The reaction gas-phase product of coupler reactor is fed between the extraction section of ester knockout tower and stripping section,
The liquid phase dimethyl oxalate. counter current contacting for rising to extraction section and flowing downward, extraction section bottom liquid phases to
Under flow to stripping section, through stripping section separate after, tower reactor obtains dimethyl oxalate. and dimethyl carbonate
Mixed liquor, the gaseous stream rising absorption Duan Zhiyu at the top of extraction section Jing after dimethyl oxalate. absorption is from ester
The methanol counter current contacting that tower top flows downward is separated, the oxalic acid diformazan carried in gas phase is further absorbed
Ester, ester are separated tower top and obtain being substantially free of dimethyl oxalate. and be recycled to the gaseous phase materials of dimethyl carbonate
Oxidative esterification regeneration unit methyl nitrite.
Preferably, the height ratio of the absorber portion, extraction section and stripping section is 1:(0.5-5):(0.2-5),
Also preferably 1:(1.5-3.5):(1-2).
Equally, the filler used in the ester knockout tower can be regular or dumped packing, the tower
Plate is valve plate, sieve plate, double pass tray, bubble cap plate or Thorman tray.
Preferably, the stripping section theoretical cam curve is 5-40 blocks, more preferably 10-25 blocks.
Methanol is used only as unlike absorbent from the dimethyl oxalate. knockout tower in existing process, it is of the invention
Ester knockout tower increased extraction section, dimethyl oxalate. serve not only as extractant separating dimethyl carbonate and
Methanol, while also serving as absorbent absorbs gas phase dimethyl oxalate..Newly-increased dimethyl oxalate. absorbs,
Reduce the consumption for absorbing methanol, at the same also can guarantee that in coupling reaction gas-phase product dimethyl carbonate with
In the case that dimethyl oxalate. is substantially completely absorbed, the tower bottoms of ester knockout tower does not contain methanol, thus
Reduce the energy consumption of subsequent separation system and the loss of methanol.
The 50-90% of the dimethyl oxalate. product obtained according to the present invention, the step c), preferably
60-85%, further preferably 60-70% are recycled to ester knockout tower as the extractant.Preferably, it is described
The temperature of extractant is 55-210 DEG C, preferably 60-150 DEG C.It is used as the dimethyl oxalate. Jing of extractant
Heat exchanger is cooled to said temperature scope and enters ester knockout tower again.Favors low temperature is in reduction extractant oxalic acid two
The consumption of methyl ester, but under normal pressure, dimethyl oxalate. freezing point is 54 DEG C, and too low temperature has oxalic acid
The risk of dimethyl ester Crystallization Plugging pipeline.
In the process of the test of the present invention, the present inventor is to extractant dimethyl oxalate in preparation concentration to methanol
Impact to dimethyl carbonate relative volatility is studied.It was found that in the method according to the invention
In, ester knockout tower extraction section liquid phase dimethyl oxalate in preparation molar concentration preferably >=20%, such as 20-90%.
Under aforementioned range, methanol and dimethyl carbonate can avoid azeotropic point, so as to relatively easily be separated.
Ester knockout tower extraction section liquid phase dimethyl oxalate in preparation molar concentration can be by adjusting extraction agent flux and tower
The ratio containing methanol stream flow of top addition is adjusting.
Preferred embodiment of the invention, the operating pressure of the ester knockout tower is
0.1-0.4MPa, preferably 0.11-0.25MPa, tower top temperature 0-60 DEG C, preferably 20-40 DEG C.
Ester knockout tower operating pressure should not be too high, and the higher bottom temperature of tower pressure is higher, is unfavorable for tower reactor oxalic acid two
Methyl ester is stablized, but ester separates the pressure limit of the operating pressure by cycle gas system of tower top, suitable malleation
Operation.
Preferred embodiment of the invention, be passed through in the ester knockout tower containing methanol stream and institute
The volume ratio for stating extractant stream is 1:(1-5), preferably 1:(1-3).
Preferred embodiment of the invention, the operating pressure of the dimethyl oxalate. treating column
0-0.3Mpa, tower top temperature 20-130 DEG C.It is highly preferred that pressure 0.1-0.2Mpa, tower top temperature
80-110℃。
Preferably, the number of theoretical plate of the dimethyl oxalate. treating column is 10-60 blocks, and reflux ratio is
2-200.It is highly preferred that number of theoretical plate is 25-50 blocks, reflux ratio 5-50.
As the reaction stream of the inventive method, the reaction mass containing CO and methyl nitrite
Can include：The methyl nitrite of the CO of 5-40%, 5-30%, the NO of 1-10%, 0.1-10%'s
Methanol, and the noble gases of surplus such as N2, in mole percent.Preferably, into coupling
The phase feed mole containing CO, methyl nitrite of reactor is consisted of：CO 10-30%, nitrous
Sour methyl ester 5-20%, NO 2-8%, methanol 1-8%, remaining is N2.Wherein methyl nitrite can be with
There is provided by oxidative esterification device.
Preferably, the reaction temperature of coupler reactor is 90-150 DEG C, and reaction pressure is 0.1-1Mpa.
Preferably, the reaction temperature of the coupler reactor is 110-130 DEG C, and reaction pressure is
0.2-0.5Mpa.In both sides method provided by the present invention, the reaction condition of coupler reactor can
With identical.Due to the strongly exothermic property of coupling reaction, the higher reaction of methyl nitrite concentration is more violent, such as
Fruit reaction heat effectively cannot be removed, and will cause reactor temperature runaway；Methyl nitrite concentration is lazy when too low
Property component concentration increase, the energy consumption of system can be increased.In addition, the presence of NO can suppress to be coupled instead
Speed is answered, so being not easy to too high, but the concentration of NO is relevant with oxidative esterification unit, is to ensure oxygen
The reaction completely of gas, NO must be excessive.As the regenerative process of methyl nitrite needs to use methanol,
Methanol in coupler reactor entrance gas phase be vapor liquid equilibrium composition, although methanol to coupling reaction not
Profit, but in order to reduce methanol content, it is necessary to the product of the regenerative response of methyl nitrite is cooled to more
Low temperature, also necessarily increases system energy consumption.
Preferred embodiment of the invention, coupler reactor adopt calandria type fixed bed reactor,
What reaction mass flowed between Bottomhole pressure, pipe is saturation water.CO is coupled dimethyl oxalate. reaction processed
It is a strong exothermal reaction, calandria type fixed bed reactor can preferably remove reaction heat, using full
Substantial amounts of heat can be absorbed with the gasification of water, while by-product low-pressure steam, advantageously reduces recirculated water use
Amount, maintains water temperature constant, while the water energy of fluidized state enough provides bigger heat transfer coefficient, is conducive to
Reaction heat is removed.
Preferred embodiment of the invention, ester knockout tower have reboiler and overhead condenser.Tower top
Condenser reduce the outer absorption methanol usage mended, tower reactor reboiler is then by the absorbing liquid of extraction section bottom
In methanol stripper, it is to avoid the methanol loss that methanol is brought with dimethyl carbonate extraction.
Preferred embodiment of the invention, the tower bottoms of ester knockout tower consist of dimethyl carbonate
0.05-5%, remaining is substantially dimethyl oxalate.；It is highly preferred that dimethyl carbonate accounts for 0.1-3%.
According to the method that the present invention is provided, while ester knockout tower absorber portion absorbs gas phase dimethyl oxalate.
Use as rectifying section, suppress dimethyl oxalate. to move to tower top.Extraction section also plays the work of absorber portion
With only in extraction section, liquid phase dimethyl oxalate. absorbs the gas phase oxalic acid two in ascending vapor first
Methyl ester and dimethyl carbonate, can be greatly lowered the usage amount of absorber portion absorbent methanol, and methanol is used
Amount is reduced, and reboiler and condenser duty are reduced.
The production dimethyl oxalate. provided using the present invention the method for by-product dimethyl carbonate, are eliminated
Cooling and alcohol cleaning device, the absorption by coupled product in prior art in cooling device and set in distillation
Two unit operations of rectification in standby are completed in focusing on an ester knockout tower, reduce energy consumption, equipment
Simplify；Prevent dimethyl oxalate. from crystallizing in cooling device, improve the yield of dimethyl oxalate.；Save
Equipment investment and floor space；Meanwhile, the simplification of flow process also greatly reduces the expense of insulation heat tracing.
Simultaneously as destroying methanol and carbonic acid by the use of system circulation as the liquid phase dimethyl oxalate. of extractant
The azeotropic balance of dimethyl ester, by dimethyl carbonate and separating methanol, then to dimethyl carbonate and oxalic acid two
Methyl ester is separated, and not only reduces the separating energy consumption of dimethyl carbonate, be also obtained reach purity will
The dimethyl carbonate asked and dimethyl oxalate. product.Simultaneously as having separated dimethyl carbonate, separate
The methanol flowed out in tower will not affect which to continue with because dimethyl carbonate is accumulated.
Using production dimethyl oxalate. the technical scheme of by-product dimethyl carbonate of the present invention, oxalic acid two
The response rate of methyl ester is more than 99.5%, and the removal efficiency of dimethyl carbonate is more than 99%, can be greatly lowered
The steam consumption of dimethyl carbonate separation process, achieves preferable technique effect.
Description of the drawings
Fig. 1 is the method according to the production dimethyl oxalate. for providing of the invention by-product dimethyl carbonate
Schematic flow sheet.
In Fig. 1,21 is coupler reactor, and 22 is ester knockout tower, and 22a is absorber portion, and 22b is extraction
Section is taken, 22c is stripping section, and 23 is dimethyl oxalate. treating column, and 24 is dimethyl oxalate. cooler,
25 is coupler reactor feed pipe, and 26 is coupler reactor discharge pipe, and 27 is that ester separates tower top
Gas phase pipeline, 28 is methanol feed pipe, and 29 is that ester separates tower bottoms pipeline, and 30 is oxalic acid diformazan
The refined tower top dimethyl carbonate pipeline of ester, 31 is oxalate product discharge pipeline, and 32 are circulation oxalic acid
Dimethyl ester pipeline, the circulation dimethyl oxalate. pipeline after 33 coolings.
Fig. 2 is that the dimethyl oxalate. concentration in ester knockout tower is relatively volatile to dimethyl carbonate with methanol
Degree distribution curve.
In Fig. 1, the phase feed containing CO, methyl nitrite enters coupler reactor by pipeline 25
21, coupler reactor discharging Jing pipeline 26 enters extraction section 22b and the stripping section of ester knockout tower 22
Between 22c, with the oxalic acid two for being entered the flowing of ester knockout tower extraction section 22b top down by pipeline 33
Methyl ester counter current contacting, the logistics obtained in the extraction section 22b bottom of ester knockout tower go ester knockout tower stripping
Section 22c, after the stripping of stripping section 22c, separates from the stripping section 22c bottoms of ester knockout tower
Treating column 23 is entered by pipeline 29 to dimethyl oxalate. with dimethyl carbonate mixed liquor.Extraction section 22b
The gaseous stream Jing after dimethyl oxalate. absorbs that top obtains, enters ester knockout tower with by pipeline 28
The methanol counter current contacting of absorber portion 22a top downs flowing, carries oxalic acid two in further absorbing gas phase
Methyl ester, ester separate tower top and obtain being substantially free of the gaseous phase materials 27 of dimethyl oxalate. and dimethyl carbonate
Deoxidation esterification regeneration methyl nitrite.
The dimethyl carbonate Jing pipeline 30 isolated at the top of dimethyl oxalate. treating column 23 is produced, tower reactor
High-purity oxalic acid dimethyl ester is obtained, dimethyl oxalate. partial material Jing pipeline 32 goes dimethyl oxalate. cold
But after device cooling, Jing pipelines 33 loop back ester knockout tower 22 as extract, dimethyl oxalate. product by
Pipeline 31 is produced.
The invention will be further elaborated below in conjunction with the accompanying drawings and by embodiment, it should be appreciated that this
Bright scope is not limited to this.
Specific embodiment
【Embodiment 1】
Phase feed containing CO, methyl nitrite enters coupler reactor 21 by pipeline 25, even
Connection reactor discharging Jing pipelines 26 are entered between extraction section 22b and the stripping section 22c of ester knockout tower 22,
With the dimethyl oxalate. absorbing liquid for being entered the flowing of ester knockout tower extraction section 22b top down by pipeline 33
Counter current contacting, the absorbing liquid logistics obtained in the extraction section 22b bottom of ester knockout tower go ester knockout tower to carry
A section 22c is evaporated, after the stripping of stripping section 22c, is separated from the stripping section 22c bottoms of ester knockout tower
Obtain dimethyl oxalate. and treating column 23 is entered by pipeline 29 with dimethyl carbonate mixed liquor.Extraction section 22b
The gaseous stream Jing after dimethyl oxalate. absorbs that top obtains, enters ester knockout tower with by pipeline 28
The methanol counter current contacting of absorber portion 22a top downs flowing, carries oxalic acid two in further absorbing gas phase
Methyl ester, ester separate tower top and obtain being substantially free of the gaseous phase materials 27 of dimethyl oxalate. and dimethyl carbonate
Deoxidation esterification regeneration methyl nitrite.
The dimethyl carbonate Jing pipeline 30 isolated at the top for the treatment of column 23 is produced, and tower reactor obtains high-purity
Dimethyl oxalate., dimethyl oxalate. partial material is Jing after pipeline 32 goes the cooling of dimethyl oxalate. cooler
Jing pipelines 33 loop back ester knockout tower 22 as extract, and dimethyl oxalate. product is adopted by pipeline 31
Go out.
The reaction temperature of coupler reactor is 120 DEG C, and reaction pressure is 0.3Mpa.
Ester knockout tower absorber portion and extraction section ratio 1:3, stripping section theoretical cam curve is 10 pieces；Operation
Pressure is 0.16Mpa；Tower top operation temperature is 38 DEG C, and tower reactor operation temperature is 177 DEG C；Extractant
(dimethyl oxalate .) logistics is 1.2 with the volume ratio of absorbent (methanol) logistics:1.
40 pieces of dimethyl oxalate. treating column number of theoretical plate, reflux ratio 6；Operating pressure 0.12Mpa；Tower
Top operation temperature is 95 DEG C, and tower reactor operation temperature is 176 DEG C；Circulate the oxalic acid diformazan as extractant
The ratio of ester and dimethyl oxalate. product is 1.3:1；Dimethyl oxalate. extractant Jing heat exchangers are cooled to
80℃。
In this embodiment, dimethyl oxalate. concentration and methanol be have studied in ester knockout tower to carbonic acid diformazan
Relation between ester relative volatility, as a result as shown in Figure 2.Fig. 2 is the oxalic acid two in ester knockout tower
Methyl acetate concentrations distribution curve is with methanol to dimethyl carbonate relative volatility distribution curve.Wherein theoretical plate
Position numerical value represents the column plate of the top-to-bottom of ester knockout tower from small to large successively.In extraction section (extraction
Take below the theoretical plate of agent charging aperture), dimethyl oxalate. molar concentration increases to 28% in the liquid phase
In the case of, dimethyl oxalate. is obvious as the effect of extractant, makes phase of the methanol to dimethyl carbonate
1.8 are increased to from the 0.7 of absorber portion (more than the theoretical plate of extractant feed) to volatility, across
Relative volatility cannot detached azeotropic point for 1.Dimethyl carbonate is from light group with methanol formation azeotropic
Divide and be changed into heavy constituent, toward tower reactor movement, methanol is then moved to tower top, and dimethyl carbonate and methanol can
It is easier to separate.
Under conditions of the present embodiment, the dimethyl oxalate. response rate is more than 99.99%, dimethyl carbonate
Removal efficiency 99.6%.Ester knockout tower is respectively 7.667MW with dimethyl oxalate. treating column reboiler
With 1.256MW.
Wherein, shown in the logistics composition table 1 in reactor feed and main pipe.
Table 1
【Embodiment 2】
With【Embodiment 1】Embodiment is identical, except for the difference that the device parameter of tower and operating condition.
The reaction temperature of coupler reactor is 120 DEG C, and reaction pressure is 0.3Mpa.
Ester knockout tower absorber portion and extraction section ratio 1:1.5, stripping section theoretical cam curve is 25 pieces；
Operating pressure is 0.16Mpa；Tower top operation temperature is 38 DEG C, and tower reactor operation temperature is 180 DEG C；Extraction
The volume ratio that agent (dimethyl oxalate .) logistics is taken with absorbent (methanol) logistics is 2.2:1.
40 pieces of dimethyl oxalate. treating column number of theoretical plate, reflux ratio 8.5；Operating pressure 0.12Mpa；
Tower top operation temperature is 96 DEG C, and tower reactor operation temperature is 176 DEG C；Dimethyl oxalate. extractant and oxalic acid
The ratio of dimethyl ester product is 2.3:1；Dimethyl oxalate. extractant Jing heat exchangers are cooled to 100 DEG C.Ester
Knockout tower extraction section liquid phase dimethyl oxalate in preparation molar concentration is 42%.
The dimethyl oxalate. response rate is more than 99.99%, dimethyl carbonate removal efficiency 99.5%.Ester is separated
Tower is respectively 8.945MW and 1.543MW with dimethyl oxalate. treating column reboiler.
Wherein, the logistics composition in reactor feed and main pipe is as shown in table 2.
Table 2
【Embodiment 3】
With【Embodiment 1】Embodiment is identical, except for the difference that feed composition, reaction condition and tower
Device parameter and operating condition.
The reaction temperature of coupler reactor is 130 DEG C, and reaction pressure is 0.4Mpa.
Ester knockout tower absorber portion and extraction section ratio 1:2, stripping section theoretical cam curve is 15 pieces；Behaviour
Make pressure for 0.2Mpa；Tower top operation temperature is 42 DEG C, and tower reactor operation temperature is 186 DEG C；Extraction
Agent (dimethyl oxalate .) logistics is 1.8 with the volume ratio of absorbent (methanol) logistics:1.
30 pieces of dimethyl oxalate. treating column number of theoretical plate, reflux ratio 8.8；Operating pressure 0.20Mpa；
Tower top operation temperature is 113 DEG C, and tower reactor operation temperature is 193 DEG C；Dimethyl oxalate. extractant and grass
The ratio of dimethyl phthalate product is 1.9:1；Dimethyl oxalate. extractant Jing heat exchangers are cooled to 60 DEG C.
Ester knockout tower extraction section liquid phase dimethyl oxalate in preparation molar concentration is 36%.
The dimethyl oxalate. response rate is more than 99.99%, dimethyl carbonate removal efficiency 99.5%.Ester is separated
Tower is respectively 9.459MW and 1.741MW with dimethyl oxalate. treating column reboiler.
Wherein, the logistics composition in reactor feed and main pipe is as shown in table 3.
Table 3
【Comparative example 1】
With【Embodiment 1】Identical scale, similar reaction condition, using patent application
Device disclosed in CN101190884A (entire contents are incorporated by reference into herein), is coupled
Product first utilizes a large amount of methanol absorptions, the weight of the tower bottoms for obtaining to consist of first in alcohol washes tower
Alcohol content 40%, dimethyl carbonate 1.1%, dimethyl oxalate. 58.9%.The total theoretical plate of alcohol recovery tower
Number is 80 pieces, and reboiler is 28.134MW, and dibasic acid esters knockout tower selects same as Example 1
Number of theoretical plate, reboiler is 1.872MW, hence it is evident that be higher than【Embodiment 1】Ester knockout tower
With the reboiler of dimethyl oxalate. treating column.
Additionally, the equipment investment in patent application CN101190884A is higher than for the offer that carries out an invention
Method equipment investment.
Claims (10)
1. a kind of method for producing dimethyl oxalate. by-product dimethyl carbonate, comprises the following steps：
A) reaction mass containing CO and methyl nitrite is passed through in coupler reactor, in platinum family
React in the presence of metallic catalyst, obtain the gaseous state containing dimethyl oxalate. and dimethyl carbonate
Logistics；
B) gaseous stream containing dimethyl oxalate. and dimethyl carbonate is passed through in ester knockout tower,
With enter from ester separation column containing methanol stream and from ester separate midsection entrance containing oxalic acid two
Methyl ester extractant stream counter current contacting, separates column overhead and obtains crude carbinol, and tower reactor is obtained comprising oxalic acid
The mixture of dimethyl ester and dimethyl carbonate；With
C) mixture is passed through in dimethyl oxalate. treating column, tower top obtains dimethyl carbonate product
Product, tower reactor obtain dimethyl oxalate. product；
Wherein, the gaseous stream containing dimethyl oxalate. and dimethyl carbonate is being passed through ester knockout tower
Before without supercooling.
2. the method for producing dimethyl oxalate. by-product dimethyl carbonate according to claim 1,
Characterized in that, the gaseous stream containing dimethyl oxalate. and dimethyl carbonate is separated being passed through ester
Tower is washed without alcohol before tower.
3. the method for producing dimethyl oxalate. by-product dimethyl carbonate according to claim 1,
Characterized in that, the ester knockout tower includes absorber portion, extraction section and stripping section；
The stripping section is located between the charging aperture of the gaseous stream and ester knockout tower tower reactor, and is filled
There are column plate or filler；
The extraction section is located at the charging aperture of the charging aperture of the gaseous stream and the extractant stream
Between, and it is filled with column plate or filler；
The absorber portion is located at the charging aperture of the extractant stream and the charging containing methanol stream
Between mouthful, and column plate or filler are housed.
4. the method for producing dimethyl oxalate. by-product dimethyl carbonate according to claim 3,
Characterized in that, the height ratio of the absorber portion, extraction section and stripping section is 1:(0.5-5):(0.2-5)；
Described filler be regular or dumped packing, the column plate be valve plate, sieve plate, double pass tray,
Bubble cap plate or Thorman tray；And/or the stripping section theoretical cam curve is 5-40 blocks.
5. the method for producing dimethyl oxalate. by-product dimethyl carbonate according to claim 1,
Characterized in that, the 50-90% of dimethyl oxalate. that the step c) is obtained is recycled to ester knockout tower
As the extractant；And/or the temperature of the extractant is 55-210 DEG C.
6. the method for producing dimethyl oxalate. by-product dimethyl carbonate according to claim 5,
Characterized in that, extraction section liquid phase dimethyl oxalate in preparation molar concentration >=20% of the ester knockout tower.
7. the method for producing dimethyl oxalate. by-product dimethyl carbonate according to claim 1,
Characterized in that, the tower top operating pressure of the ester knockout tower is 0.1-0.4Mpa, tower top temperature
0-60℃。
8. the method for producing dimethyl oxalate. by-product dimethyl carbonate according to claim 1,
Characterized in that, being passed through the body containing methanol stream with the extractant stream in the ester knockout tower
Product is than being 1:(1-5).
9. the method for producing dimethyl oxalate. by-product dimethyl carbonate according to claim 1,
Characterized in that, operating pressure 0-0.3Mpa of the dimethyl oxalate. treating column, tower top temperature
20-130℃；And/or the number of theoretical plate of the dimethyl oxalate. treating column be 10-60 blocks, reflux ratio
For 2-200.
10. the method for producing dimethyl oxalate. by-product dimethyl carbonate according to claim 1,
Characterized in that, in mole percent, the reaction mass bag containing CO and methyl nitrite
Include：The methyl nitrite of the CO of 5-40%, 5-30%, the NO of 1-10%, the methanol of 0.1-10%,
And the noble gases of surplus.
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| CN112174821A (en) * | 2020-09-04 | 2021-01-05 | 中盐安徽红四方股份有限公司 | Rectification method of dimethyl oxalate |
| CN112409181A (en) * | 2020-12-10 | 2021-02-26 | 新疆天业汇合新材料有限公司 | Dimethyl oxalate rectifying device for coal chemical industry |
| CN112479869A (en) * | 2020-12-10 | 2021-03-12 | 新疆天业汇合新材料有限公司 | Method for rectifying dimethyl oxalate in coal chemical industry |
| CN112679349A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Refining method and system for mixed material flow containing dimethyl oxalate |
| CN113754539A (en) * | 2021-10-11 | 2021-12-07 | 天津博创工程科技有限公司 | Purification and decoloration method of dimethyl oxalate |
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| CN203960094U (en) * | 2014-07-03 | 2014-11-26 | 中国石油化工股份有限公司 | The production equipment of dimethyl oxalate |
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| CN112679349A (en) * | 2019-10-18 | 2021-04-20 | 中国石油化工股份有限公司 | Refining method and system for mixed material flow containing dimethyl oxalate |
| CN112679349B (en) * | 2019-10-18 | 2023-04-07 | 中国石油化工股份有限公司 | Refining method and system for mixed material flow containing dimethyl oxalate |
| CN112174821A (en) * | 2020-09-04 | 2021-01-05 | 中盐安徽红四方股份有限公司 | Rectification method of dimethyl oxalate |
| CN112174821B (en) * | 2020-09-04 | 2023-08-18 | 中盐安徽红四方股份有限公司 | Rectification method of dimethyl oxalate |
| CN112409181A (en) * | 2020-12-10 | 2021-02-26 | 新疆天业汇合新材料有限公司 | Dimethyl oxalate rectifying device for coal chemical industry |
| CN112479869A (en) * | 2020-12-10 | 2021-03-12 | 新疆天业汇合新材料有限公司 | Method for rectifying dimethyl oxalate in coal chemical industry |
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| CN113754539A (en) * | 2021-10-11 | 2021-12-07 | 天津博创工程科技有限公司 | Purification and decoloration method of dimethyl oxalate |
| CN113754539B (en) * | 2021-10-11 | 2024-01-12 | 天津博创工程科技有限公司 | Purification and decolorization method of dimethyl oxalate |
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