CN106431920B - The method that synthesis gas prepares dimethyl oxalate and by-product dimethyl carbonate - Google Patents
The method that synthesis gas prepares dimethyl oxalate and by-product dimethyl carbonate Download PDFInfo
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- CN106431920B CN106431920B CN201610694416.7A CN201610694416A CN106431920B CN 106431920 B CN106431920 B CN 106431920B CN 201610694416 A CN201610694416 A CN 201610694416A CN 106431920 B CN106431920 B CN 106431920B
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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
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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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
Abstract
The present invention relates to a kind of methods that synthesis gas prepares dimethyl oxalate and by-product dimethyl carbonate, mainly solve the problems, such as that energy consumption is higher in the prior art, the cycle of operation is shorter, product loss amount is higher.A kind of method that the present invention prepares dimethyl oxalate and by-product dimethyl carbonate by using synthesis gas, send the material of synthesis gas coupling reaction to oxalate recovery tower, tower top is without dimethyl carbonate to reduce return tolerance, kettle material send oxalate product tower, compared under low operating temperature, the technical solution that tower reactor obtains dimethyl oxalate preferably solves the above problem, can be used for synthesis gas and prepares in dimethyl oxalate.
Description
Technical field
The present invention relates to a kind of methods that synthesis gas prepares dimethyl oxalate and by-product dimethyl carbonate.
Background technique
Dimethyl oxalate (COOCH3)2It is important industrial chemicals, it can hydrogenated reduction reaction generation ethylene glycol.Traditional grass
Dimethyl phthalate synthetic method carries out esterification using oxalic acid and methanol and obtains, and still, this method is in the presence of energy consumption is high, pollution
The problems such as serious and raw material availability is low.Thus, nowadays all prepared using synthesis gas oxidative esterification reaction, coupling reaction two step method
Dimethyl oxalate.First with methanol CH3OH and oxygen O2As raw material, with the nitric oxide NO being recycled back into and since pair occurs
It reacts and consumes the fresh methyl nitrite CH that loss requires supplementation with3Oxidative esterification reaction occurs together and obtains nitrous acid first by ONO
Ester.Then the synthesis gas of methyl nitrite and the CO containing carbon monoxide carry out gas-phase catalytic coupling under the action of coupling catalyst
Reaction generates dimethyl oxalate product.Meanwhile side reaction also occurs and generates dimethyl carbonate (CH3O)2CO byproduct.In addition,
Containing carbon monoxide and hydrogen H2Synthesis gas existence condition under, also generation side reaction generate methyl formate HCOOCH3Byproduct.
Main reaction equation are as follows:
2CH3OH+2NO+1/2O2→2CH3ONO+H2O
2CH3ONO+2CO→(COOCH3)2+2NO
Two side reaction equations are as follows:
2CH3ONO+CO→(CH3O)2CO+2NO
CH3ONO+CO+1/2H2→HCOOCH3+NO
The critical nature of raw material and product is as follows:
The method of number of patent application CN201010146892.8CO preparing oxalate by coupling reaction proposes raw material of synthetic gas reaction
Generate raw material ratio, reaction condition and the Conversion Selectivity of dimethyl oxalate.Number of patent application 200910057836.4 produces grass
The method of the method and number of patent application 200910057844.9CO preparing oxalate by coupling reaction of acid esters is each provided with production oxalic acid two
The preparation process of catalyst needed for methyl esters technique and the technical solution for preparing dimethyl oxalate.
The method of a kind of synthesizing dimethyl oxalate of number of patent application CN200610118543.9 and by-product dimethyl carbonate, mentions
More perfect process flow is gone out, the feed separation of reactor product purification is using dimethyl oxalate as extractant, extraction
After taking rectifying to isolate whole methanol, further separation of dimethyl oxalate and dimethyl carbonate.
A kind of process flow for producing ethylene glycol with coproduction product dimethyl carbonate of number of patent application CN200810043079.0, it is public
The continuous process by carbon monoxide for initial feed synthesizing glycol and co-producing dimethyl carbonate is opened.
Double-column process separating low concentration carbonic acid in number of patent application CN200810201737.4 dimethyl oxalate synthesis process
The method of dimethyl ester discloses the production technology of separation of dimethyl oxalate, dimethyl carbonate, methanol, makes Methanol Recovery and recycles
It uses.
The recovery method of number of patent application CN201210424128.1 synthesis gas preparing ethylene glycol process dimethyl oxalate in preparation, it is public
It has opened in Batch Process operational process, the method for avoiding dimethyl oxalate Crystallization Plugging pipeline.
The production method of number of patent application CN201410314462.0 dimethyl oxalate describes and carries out being coupled first instead
It answers, then carries out feed separation and obtain the technical solution of dimethyl oxalate product.
Number of patent application CN201410353158.7 commercial syngas pressure carbonylation produces dimethyl oxalate and adds hydrogen second
The technique and apparatus system of glycol, a kind of commercial syngas of number of patent application CN201420296748.6 produce ethylene glycol with coproduction product
The apparatus system of dimethyl carbonate, number of patent application CN201420408878.4 commercial syngas pressure carbonylation produce oxalic acid diformazan
Ester and the apparatus system for adding hydrogen preparing ethylene glycol disclose and produce dimethyl oxalate using raw material of synthetic gas and add hydrogen production second two
The process flow of alcohol.
In the prior art, number of patent application CN201010146892.8 and number of patent application CN200910057836.4 and
The reaction process and process that number of patent application CN200910057844.9 discloses production dimethyl oxalate do not have still
There is the concrete technology method that separation of dimethyl oxalate and dimethyl carbonate is set forth in detail, also lacks separating-purifying and refine oxalic acid diformazan
The technical solution of ester product.
Number of patent application CN200610118543.9, number of patent application CN200810043079.0, number of patent application
CN200810201737.4, number of patent application CN201210424128.1, number of patent application CN201410314462.0, patent Shen
Please number CN201410353158.7, number of patent application CN201420296748.6, number of patent application CN201420408878.4 it is equal
The technical solution of separating-purifying purification dimethyl oxalate is disclosed, the rectifying knockout tower tower reactor in these technical solutions is available
Dimethyl oxalate product, process operation parameter are as follows:
| Serial number | Number of patent application | Knockout tower device name | Operating pressure MPa | Bottom temperature DEG C |
| 1 | CN200610118543.9 | Dibasic acid esters knockout tower | 0.05~0.20 | 120~180 |
| 2 | CN200810043079.0 | Destilling tower 4 | Normal pressure | 145 |
| 3 | CN200810201737.4 | Dimethyl oxalate knockout tower T101 | 0.1013 | 163.7 |
| 4 | CN201210424128.1 | Rectifying column (1) | 0.066 | 140~150 |
| 5 | CN201410314462.0 | Dimethyl oxalate recovery tower C101 | 0.14~0.25 | 170~200 |
| 6 | CN201410353158.7 | DMO rectifying column 6 | Normal pressure or decompression | 120~200 |
| 7 | CN201420296748.6 | DMO rectifying column 6 | Normal pressure or decompression | 120~200 |
| 8 | CN201420408878.4 | DMO rectifying column 6 | Normal pressure or decompression | 120~200 |
Above-mentioned dimethyl oxalate rectifying knockout tower bottom temperature between 120~200 DEG C, accordingly process operation parameter into
During row industrialization large-scale production dimethyl oxalate product, when bottom temperature is at 139~200 DEG C, easily tie
Burnt phenomenon, technique process units are difficult to long period even running at full capacity.Meanwhile nitric oxide is recycled back into gas containing carbonic acid two
Methyl esters, methyl nitrite, methyl formate and recycle methanol, a part of prior art use conventional rectification partition method, but this method
It is used only for laboratory scale or intermittently operated, and is applied on the technique process units for industrializing extensive continuous operation, is deposited
In " enlarge-effect "；Another part prior art is separated using extraction fractional distillation, but this method working efficiency is low, energy consumption
It is high.In addition, dimethyl carbonate is contacted with water occurs hydrolysis, generates acidification phenomenon and corrode equipment.
The prior art exists as a result: (1) dimethyl oxalate coking, and the technique process units cycle of operation reduces；(2) it returns
Gas circular flow is big, and operation operation energy consumption is high；(3) dimethyl carbonate hydrolyzes, equipment acidizing corrosion；(4) dimethyl oxalate coking
The problems such as being hydrolyzed with dimethyl carbonate, dimethyl oxalate product and dimethyl carbonate byproduct caused to lose.
Summary of the invention
That the technical problem to be solved by the present invention is to energy consumptions in the prior art is higher, the cycle of operation is shorter, product loss amount
Higher problem provides a kind of method that new synthesis gas prepares dimethyl oxalate and by-product dimethyl carbonate.This method has
The advantage that energy consumption is lower, the cycle of operation is longer, product loss amount is lower.
To solve the above problems, The technical solution adopted by the invention is as follows: a kind of synthesis gas prepares dimethyl oxalate and pair
The method for producing dimethyl carbonate, by methanol (01), fresh methyl nitrite (02) and oxygen (03) and oxalate recovery tower
(105) light component containing nitric oxide of tower top outflow is recycled back into gas (09), is respectively fed to oxidative esterification reaction rectifying column
(101), oxidative esterification reaction occur in the oxidative esterification reaction rectifying column (101) obtain include methyl nitrite light component
(04), light component (04) is flowed out from oxidative esterification reaction rectifying column (101) tower top, and it is anti-to enter coupling together with carbon monoxide (05)
Device (104) are answered, under the action of coupling catalyst, carry out gas-phase catalytic coupling reaction to generate including dimethyl oxalate, carbonic acid two
The product of methyl esters, methyl formate；The material (06) flowed out from coupler reactor (104) is sent to oxalate recovery tower (105), methanol
Detergent (07) is sent into from oxalate recovery tower (105) tower top, and material (06) is by oxalate recovery tower (105) absorption distillation point
From overhead components are sent into oxidative esterification reaction rectifying column (101) through compressor (103) pressurization to be recycled back into gas (09)；Oxalic acid
The material (08) including dimethyl oxalate, dimethyl carbonate and methanol of ester recovery tower (105) tower reactor separation outflow enters oxalic acid
Ester product tower (106), after rectification under vacuum, the isolated dimethyl oxalate product (10) of tower reactor, tower top separation outflow includes carbon
The material (11) of dimethyl phthalate and methanol, material (11) and return material (15) enter carbon ester lower pressure column (107), and tower reactor separates
To methanol (12) cycling and reutilization, the dimethyl carbonate of tower top separation outflow and the azeotropic mixture (13) of methanol enter carbon ester pressurizing tower
(108), tower top obtains returning material (15) back to carbon ester lower pressure column (107) entrance, and tower reactor obtains dimethyl carbonate byproduct
(14)；Oxidative esterification reaction rectifying column (101) tower reactor separation outflow is sent including the heavy constituent (16) of methyl formate, water, acid to de-
Weight tower (102), the isolated methyl formate byproduct (17) of tower top；Tower reactor separation outflow includes the mixed waste liquor (18) of water, acid.
In above-mentioned technical proposal, it is preferable that oxidative esterification reaction rectifying column (101) is plate column or packed tower, is not needed
Catalyst, 0.25~0.55MPa of operating pressure, 0~30 DEG C of tower top operation temperature, 45~75 DEG C of reaction temperature, tower reactor operation temperature
75~105 DEG C of degree, methanol: mass ratio=5.0 of oxygen~40.0:1, fresh methyl nitrite: mass ratio=0.05 of oxygen
~0.35:1.
In above-mentioned technical proposal, it is preferable that weight-removing column (102) 0.25~0.45MPa of operating pressure, tower top operation temperature 75
~100 DEG C, 115~145 DEG C of tower reactor operation temperature, reflux ratio 0.8~5.8.
In above-mentioned technical proposal, it is preferable that compressor (103) entry operation 0.05~0.35MPa of pressure, operation temperature 5
~45 DEG C, export operation 0.25~0.55MPa of pressure, 25~65 DEG C of operation temperature.
In above-mentioned technical proposal, it is preferable that coupler reactor (104) is calandria type fixed bed reactor, using support type
Palladium catalyst, palladium load quality content are 0.50%~3.50%, aluminium oxide Al2O3Carrier, 0.15~0.45MPa of operating pressure,
100~140 DEG C of operation temperature, carbon monoxide: mass ratio=1.0 of oxygen~5.5:1.
In above-mentioned technical proposal, it is preferable that oxalate recovery tower (105) 0.10~0.60MPa of operating pressure, tower top operation
40~115 DEG C of temperature, 95~145 DEG C of tower reactor operation temperature, reflux ratio 0.5~4.5.
In above-mentioned technical proposal, it is preferable that oxalate product tower (106) 0.005~0.035MPa of operating pressure, tower top behaviour
Make 15~55 DEG C of temperature, 108~138 DEG C of tower reactor operation temperature, reflux ratio 0.3~3.5.
In above-mentioned technical proposal, it is preferable that carbon ester lower pressure column (107) 0.10~0.30MPa of operating pressure, tower top operation temperature
45~75 DEG C of degree, 70~110 DEG C of tower reactor operation temperature, reflux ratio 8.0~25.0.
In above-mentioned technical proposal, it is preferable that carbon ester pressurizing tower (108) 0.70~1.10MPa of operating pressure, tower top operation temperature
130~145 DEG C of degree, 165~195 DEG C of tower reactor operation temperature, reflux ratio 2.0~16.0.
Technological means of the invention is: synthesis gas coupling reaction obtains the material 06 containing dimethyl oxalate, dimethyl carbonate,
Material 06 is sent into oxalate recovery tower 105 by the first step, is optimized component separation sequence, is redefined weight key component, pass through
Methanol 07 washs, and tower top separation outflow is free of the material 09 of dimethyl carbonate, tower reactor separation outflow dimethyl oxalate, carbonic acid diformazan
Material 08 is sent into oxalate product tower 106 by ester and methanol 08, second step, rectification under vacuum lock out operation is carried out, in lower behaviour
At a temperature of work, the isolated dimethyl oxalate product 10 of tower reactor.The coking of dimethyl oxalate is efficiently avoided as a result, is reduced
It is recycled back into the flow of gas 09, the power of compressor and the energy consumption of operation operation is reduced, avoids dimethyl carbonate return
It is contacted with water and hydrolysis acidizing corrosion equipment occurs.The present invention send the material of synthesis gas coupling reaction to oxalate recovery tower,
For tower top without dimethyl carbonate to reduce return tolerance, kettle material send oxalate product tower, compared under low operating temperature, tower reactor
Obtain dimethyl oxalate.Dimethyl oxalate coking is avoided as a result, and the cycle of operation extended to 1 year from 3~6 months；Operation energy consumption drop
Low 1.4~9.8%；Dimethyl carbonate hydrolysis acidification is prevented, equipment life extended to 15~20 years from 5 years；Dimethyl oxalate and
Dimethyl carbonate loss drops to zero from annual 0.01%~0.05%, preferably solves the problems, such as this, can be applied to preparation grass
In the industrial production of dimethyl phthalate and ethylene glycol, preferable technical effect is achieved.
Detailed description of the invention
Fig. 1 is the flow diagram of the method for the invention.
In Fig. 1,01- methanol, 02- methyl nitrite, 03- oxygen, 04- light component, 05- carbon monoxide, 06- material, 07-
Methanol detergent, 08- material, 09- are recycled back into gas, 10- dimethyl oxalate product, 11- material, 12- carbon ester low pressure tower reactor
Methanol, 13- azeotropic mixture, 14- dimethyl carbonate byproduct, 15- return material, 16- heavy constituent, 17- methyl formate byproduct,
18- mixed waste liquor, 101- oxidative esterification reaction rectifying column, 102- weight-removing column, 103- compressor, 104- coupler reactor, 105-
Oxalate recovery tower, 106- oxalate product tower, 107- carbon ester lower pressure column, 108- carbon ester pressurizing tower.
The present invention will be further described below by way of examples, but is not limited only to the present embodiment.
Specific embodiment
[embodiment 1]
A kind of method that synthesis gas prepares dimethyl oxalate and by-product dimethyl carbonate, as shown in Figure 1, by methanol (01),
Fresh methyl nitrite (02) and oxygen (03) and oxalate recycling that loss requires supplementation with are consumed since side reaction occurs
The outflow of tower (105) tower top is recycled back into gas (09) containing light components such as nitric oxides, is respectively fed to oxidative esterification reaction rectifying column
(101) corresponding position occurs oxidative esterification reaction in oxidative esterification reaction rectifying column (101) and obtains methyl nitrite and its
Its component.Methyl nitrite and other light components (04) are separated from oxidative esterification reaction rectifying column (101) tower top to flow out, with an oxygen
Change carbon (05) and enter coupler reactor (104) jointly, under the action of coupling catalyst, carries out gas-phase catalytic coupling reaction and generate
Dimethyl oxalate product.Side reaction also occurs simultaneously and generates dimethyl carbonate byproduct；Furthermore exist in carbon monoxide and hydrogen
Under the conditions of, it also occur that side reaction generates methyl formate byproduct.The material (06) flowed out from coupler reactor (104) is sent to grass
Acid esters recovery tower (105), methanol detergent (07) are also sent into from oxalate recovery tower (105) tower top, and material (06) passes through oxalic acid
The separation of ester recovery tower (105) absorption distillation, tower top separation outflow nitric oxide, methyl nitrite, methyl formate and light group other
Lease making overcompression machine (103) pressurization is sent into oxidative esterification reaction rectifying column (101) to be recycled back into gas (09).Oxalate recovery tower
(105) tower reactor separation outflow dimethyl oxalate, dimethyl carbonate and methanol (08).Material (08) enters oxalate product tower
(106), after rectification under vacuum, the isolated dimethyl oxalate product (10) of tower reactor；Tower top separation outflow dimethyl carbonate and first
Alcohol (11).Since dimethyl carbonate and methanol are there are azeotropic area, material (11) needs carbon ester lower pressure column (107) and carbon ester pressurizing tower
(108) double tower system carries out joint rectifying lock out operation.Material (11) and return material (15) are first fed into carbon ester lower pressure column
(107), the isolated methanol of tower reactor (12) is recycled back into recycling；Tower top separation outflow dimethyl carbonate and methanol azeotrope
(13) enter carbon ester pressurizing tower (108), tower top material (15) returns to carbon ester lower pressure column (107) entrance；The isolated carbon of tower reactor
Dimethyl phthalate byproduct (14).Oxidative esterification reaction rectifying column (101) tower reactor separation outflow methyl formate, water, acid and other heavy
Component (16) is sent to weight-removing column (102), the isolated methyl formate byproduct (17) of tower top；Tower reactor separate outflow water, acid and its
Its heavy constituent mixed waste liquor (18).
By taking 1000 tons/year of synthesis gas of production scale prepare ethylene glycol pilot-plant as an example, pass through oxidative esterification reaction, coupling
Reaction two step method prepares dimethyl oxalate.The technology of dimethyl oxalate and by-product dimethyl carbonate is prepared using synthesis gas of the present invention
Method, the material that synthesis gas coupling reaction is obtained are sent into oxalate recovery tower, and tower top outflow is free of the material of dimethyl carbonate,
Tower reactor, which flows out material, is sent into oxalate product tower, compared under low operating temperature, the skill of the isolated dimethyl oxalate product of tower reactor
Art means reach and avoid dimethyl oxalate coking, reduce operation operation energy consumption, and dimethyl carbonate is prevented to be recycled back into hydrolysis corrosion
The technical purpose of equipment.
Technological parameter of the invention is as follows: oxidative esterification reaction rectifying column 101 is plate column, does not need catalyst, is operated
Pressure 0.35MPa, 10 DEG C of tower top operation temperature, 59 DEG C of reaction temperature, 86 DEG C of tower reactor operation temperature, methanol: the mass ratio of oxygen
=7.7:1 supplements fresh methyl nitrite: mass ratio=0.18:1 of oxygen；102 operating pressure 0.30MPa of weight-removing column, tower top
84 DEG C of operation temperature, 128 DEG C of tower reactor operation temperature, reflux ratio 3.2；103 entry operation pressure 0.28MPa of compressor, operation temperature
10 DEG C, export operation pressure 0.46MPa, 59 DEG C of operation temperature of degree；Coupler reactor 104 is calandria type fixed bed reactor, instead
Answering bore is 15 millimeters, and using load type palladium catalyst, palladium load quality content is 1.97%, aluminium oxide Al2O3Carrier, behaviour
Make pressure 0.32MPa, 110 DEG C of operation temperature, carbon monoxide: mass ratio=3.6:1 of oxygen；Oxalate recovery tower 105 operates
Pressure 0.40MPa, 66 DEG C of tower top operation temperature, 128 DEG C of tower reactor operation temperature, reflux ratio 4.1；Oxalate product tower 106 operates
Pressure 0.015MPa, 27 DEG C of tower top operation temperature, 116 DEG C of tower reactor operation temperature, reflux ratio 2.9；The operation pressure of carbon ester lower pressure column 107
Power 0.25MPa, 61 DEG C of tower top operation temperature, 103 DEG C of tower reactor operation temperature, reflux ratio 14.0；108 operating pressure of carbon ester pressurizing tower
0.98MPa, 141 DEG C of tower top operation temperature, 187 DEG C of tower reactor operation temperature, reflux ratio 11.0.
As a result, in 1 year operational process of normal full load, coking phenomenon does not occur for pilot-plant；Meanwhile nitric oxide follows
Ring returns to gas and is free of dimethyl carbonate, makes to be recycled back into throughput reduction, operation operation energy consumption decline 7.21%；Moreover, carbonic acid
Hydrolysis does not occur for dimethyl ester, and equipment is not corroded, and service life was up to 15 years；Finally, dimethyl oxalate product and carbonic acid two
Methyl esters byproduct does not also lose.
[comparative example 1]
The prior art uses synthesis gas for raw material, prepares oxalic acid diformazan by oxidative esterification reaction, coupling reaction two step method
Ester product, further prepares ethylene glycol product.During separation and purification dimethyl oxalate, rectifying knockout tower bottom temperature is equal
Between 120~200 DEG C.And when bottom temperature >=139 DEG C, coking phenomenon easily occurs for the rectifying column of heavy industrialization,
It needs parking maintenance primary within usual 3~6 months, carries out tower reactor coke cleaning treatment, process units is difficult to long period and steadily transports at full capacity
Row.Meanwhile nitric oxide is recycled back into gas and contains dimethyl carbonate, makes to be recycled back into throughput increase, compressor horsepower increases
Add, operation operation energy consumption also increases.Moreover, dimethyl carbonate return is contacted with water, make dimethyl carbonate that hydrolysis occur, produces
Raw acidification phenomenon corrodes equipment, needs within usual 5 years or so to update the equipment for being acidified corrosion.Due to dimethyl oxalate coking and
Dimethyl carbonate hydrolysis, cause dimethyl oxalate product and dimethyl carbonate byproduct lose annual about 0.01%~0.05% it
Between.
[embodiment 2]
According to condition described in embodiment 1 and step, only production scale is changed to 20,000 tons/year of synthesis gas and prepares ethylene glycol
Industrial production equipment, 104 tube inner diameter of coupler reactor are changed to 25 millimeters.Dimethyl oxalate is prepared using synthesis gas of the present invention
And the technical method of by-product dimethyl carbonate, in 1 year operational process of normal full load, it is existing that coking does not occur for industrial production equipment
As；Meanwhile nitric oxide is recycled back into gas without dimethyl carbonate, makes to be recycled back into throughput reduction, operate under operation energy consumption
Drop 7.72%；Moreover, hydrolysis does not occur for dimethyl carbonate, equipment is not corroded, and service life was up to 20 years；Finally, oxalic acid
Dimethyl ester product and dimethyl carbonate byproduct also do not lose.
[embodiment 3]
According to condition described in embodiment 1 and step, only production scale is changed to 200,000 tons/year of synthesis gas and prepares ethylene glycol
Industrial production equipment, 104 tube inner diameter of coupler reactor are changed to 32 millimeters.Dimethyl oxalate is prepared using synthesis gas of the present invention
And the technical method of by-product dimethyl carbonate, in 1 year operational process of normal full load, it is existing that coking does not occur for industrial production equipment
As；Meanwhile nitric oxide is recycled back into gas without dimethyl carbonate, makes to be recycled back into throughput reduction, operate under operation energy consumption
Drop 8.36%；Moreover, hydrolysis does not occur for dimethyl carbonate, equipment is not corroded, and service life was up to 20 years；Finally, oxalic acid
Dimethyl ester product and dimethyl carbonate byproduct also do not lose.
[embodiment 4]
According to condition described in embodiment 1 and step, only production scale is changed to 300,000 tons/year of synthesis gas and prepares ethylene glycol
Industrial production equipment, 104 tube inner diameter of coupler reactor are changed to 40 millimeters.Dimethyl oxalate is prepared using synthesis gas of the present invention
And the technical method of by-product dimethyl carbonate, in 1 year operational process of normal full load, it is existing that coking does not occur for industrial production equipment
As；Meanwhile nitric oxide is recycled back into gas without dimethyl carbonate, makes to be recycled back into throughput reduction, operate under operation energy consumption
Drop 8.36%；Moreover, hydrolysis does not occur for dimethyl carbonate, equipment is not corroded, and service life was up to 20 years；Finally, oxalic acid
Dimethyl ester product and dimethyl carbonate byproduct also do not lose.
[embodiment 5]
According to condition described in embodiment 1 and step, only production scale is changed to 400,000 tons/year of synthesis gas and prepares ethylene glycol
Industrial production equipment, 104 tube inner diameter of coupler reactor are changed to 50 millimeters.Dimethyl oxalate is prepared using synthesis gas of the present invention
And the technical method of by-product dimethyl carbonate, in 1 year operational process of normal full load, it is existing that coking does not occur for industrial production equipment
As；Meanwhile nitric oxide is recycled back into gas without dimethyl carbonate, makes to be recycled back into throughput reduction, operate under operation energy consumption
Drop 8.49%；Moreover, hydrolysis does not occur for dimethyl carbonate, equipment is not corroded, and service life was up to 20 years；Finally, oxalic acid
Dimethyl ester product and dimethyl carbonate byproduct also do not lose.
[embodiment 6]
According to condition as described in example 4 and step, production scale is still that 300,000 tons/year of synthesis gas prepare ethylene glycol industry
Process units, only technological parameter changes: oxidative esterification reaction rectifying column 101 is packed tower, does not need catalyst, operating pressure
0.25MPa, 0 DEG C of tower top operation temperature, 45 DEG C of reaction temperature, 75 DEG C of tower reactor operation temperature, methanol: mass ratio=5.0 of oxygen:
1, supplement fresh methyl nitrite: mass ratio=0.05:1 of oxygen；102 operating pressure 0.25MPa of weight-removing column, tower top operation temperature
75 DEG C of degree, 115 DEG C of tower reactor operation temperature, reflux ratio 0.8；Compressor 103 entry operation pressure 0.05MPa, 5 DEG C of operation temperature,
Export operation pressure 0.25MPa, 25 DEG C of operation temperature；Coupler reactor 104 is calandria type fixed bed reactor, tube inner diameter
It is 40 millimeters, using load type palladium catalyst, palladium load quality content is 3.50%, aluminium oxide Al2O3Carrier, operating pressure
0.15MPa, 100 DEG C of operation temperature, carbon monoxide: mass ratio=1.0:1 of oxygen；105 operating pressure of oxalate recovery tower
0.10MPa, 40 DEG C of tower top operation temperature, 95 DEG C of tower reactor operation temperature, reflux ratio 0.5；106 operating pressure of oxalate product tower
0.005MPa, 15 DEG C of tower top operation temperature, 108 DEG C of tower reactor operation temperature, reflux ratio 0.3；107 operating pressure of carbon ester lower pressure column
0.10MPa, 45 DEG C of tower top operation temperature, 70 DEG C of tower reactor operation temperature, reflux ratio 8.0；108 operating pressure of carbon ester pressurizing tower
0.70MPa, 130 DEG C of tower top operation temperature, 165 DEG C of tower reactor operation temperature, reflux ratio 2.0.It was transported as a result, at normal full load 1 year
During row, coking phenomenon does not occur for industrial production equipment；Meanwhile nitric oxide is recycled back into gas without dimethyl carbonate, makes
It is recycled back into throughput reduction, operation operation energy consumption decline 9.80%；Moreover, hydrolysis, equipment do not occur for dimethyl carbonate
Do not corrode, service life was up to 20 years；Finally, dimethyl oxalate product and dimethyl carbonate byproduct also do not lose.
[embodiment 7]
According to condition as described in example 4 and step, production scale is still that 300,000 tons/year of synthesis gas prepare ethylene glycol industry
Process units, only technological parameter changes: oxidative esterification reaction rectifying column 101 is packed tower, does not need catalyst, operating pressure
0.55MPa, 30 DEG C of tower top operation temperature, 75 DEG C of reaction temperature, 105 DEG C of tower reactor operation temperature, methanol: the mass ratio of oxygen=
40.0:1 supplements fresh methyl nitrite: mass ratio=0.35:1 of oxygen；102 operating pressure 0.45MPa of weight-removing column, tower top
100 DEG C of operation temperature, 145 DEG C of tower reactor operation temperature, reflux ratio 5.8；103 entry operation pressure 0.35MPa of compressor, operation temperature
45 DEG C, export operation pressure 0.55MPa, 65 DEG C of operation temperature of degree；Coupler reactor 104 is calandria type fixed bed reactor, instead
Answering bore is 40 millimeters, and using load type palladium catalyst, palladium load quality content is 0.50%, aluminium oxide Al2O3Carrier, behaviour
Make pressure 0.45MPa, 140 DEG C of operation temperature, carbon monoxide: mass ratio=5.5:1 of oxygen；Oxalate recovery tower 105 operates
Pressure 0.60MPa, 115 DEG C of tower top operation temperature, 145 DEG C of tower reactor operation temperature, reflux ratio 4.5；Oxalate product tower 106 operates
Pressure 0.035MPa, 55 DEG C of tower top operation temperature, 138 DEG C of tower reactor operation temperature, reflux ratio 3.5；The operation pressure of carbon ester lower pressure column 107
Power 0.30MPa, 75 DEG C of tower top operation temperature, 110 DEG C of tower reactor operation temperature, reflux ratio 25.0；108 operating pressure of carbon ester pressurizing tower
1.10MPa, 145 DEG C of tower top operation temperature, 195 DEG C of tower reactor operation temperature, reflux ratio 16.0.It was transported as a result, at normal full load 1 year
During row, coking phenomenon does not occur for industrial production equipment；Meanwhile nitric oxide is recycled back into gas without dimethyl carbonate, makes
It is recycled back into throughput reduction, operation operation energy consumption decline 1.40%；Moreover, hydrolysis, equipment do not occur for dimethyl carbonate
Do not corrode, service life was up to 20 years；Finally, dimethyl oxalate product and dimethyl carbonate byproduct also do not lose.It is above-mentioned
The material balance of 1~embodiment of embodiment 7, see the table below:
Claims (1)
1. a kind of method that synthesis gas prepares dimethyl oxalate and by-product dimethyl carbonate, by methanol (01), fresh nitrous acid first
The light component containing nitric oxide that ester (02) and oxygen (03) and oxalate recovery tower (105) tower top flow out is recycled back into gas
(09), oxidative esterification reaction rectifying column (101) are respectively fed to, oxidative esterification occurs in oxidative esterification reaction rectifying column (101)
Reaction obtain include methyl nitrite light component (04), light component (04) is from oxidative esterification reaction rectifying column (101) tower top stream
Out, enter coupler reactor (104) together with carbon monoxide (05), under the action of coupling catalyst, it is even to carry out gas phase catalysis
Connection reaction generation includes the product of dimethyl oxalate, dimethyl carbonate, methyl formate；The object flowed out from coupler reactor (104)
Material (06) is sent to oxalate recovery tower (105), and methanol detergent (07) is sent into from oxalate recovery tower (105) tower top, material
(06) it is separated by oxalate recovery tower (105) absorption distillation, overhead components are recycled back into gas through compressor (103) pressurization
(09) oxidative esterification reaction rectifying column (101) are sent into；The separation outflow of oxalate recovery tower (105) tower reactor includes oxalic acid diformazan
The material (08) of ester, dimethyl carbonate and methanol enters oxalate product tower (106), and after rectification under vacuum, tower reactor is isolated
Dimethyl oxalate product (10), tower top separation outflow include the material (11) of dimethyl carbonate and methanol, material (11) and return
Material (15) enters carbon ester lower pressure column (107), the isolated methanol of tower reactor (12) cycling and reutilization, the carbonic acid of tower top separation outflow
The azeotropic mixture (13) of dimethyl ester and methanol enters carbon ester pressurizing tower (108), and it is low back to carbon ester that tower top obtains return material (15)
Tower (107) entrance is pressed, tower reactor obtains dimethyl carbonate byproduct (14)；Oxidative esterification reaction rectifying column (101) tower reactor separation stream
Heavy constituent (16) out including methyl formate, water, acid is sent to weight-removing column (102), the isolated methyl formate byproduct of tower top
(17)；Tower reactor separation outflow includes the mixed waste liquor (18) of water, acid；Oxidative esterification reaction rectifying column (101) is plate column or fills out
Expect tower, does not need catalyst, 0.25~0.55MPa of operating pressure, 0~30 DEG C of tower top operation temperature, 45~75 DEG C of reaction temperature,
75~105 DEG C of tower reactor operation temperature, methanol: mass ratio=5.0 of oxygen~40.0:1, fresh methyl nitrite: the matter of oxygen
Measure ratio=0.05~0.35:1；Weight-removing column (102) 0.25~0.45MPa of operating pressure, 75~100 DEG C of tower top operation temperature, tower
115~145 DEG C of kettle operation temperature, reflux ratio 0.8~5.8；Compressor (103) entry operation 0.05~0.35MPa of pressure, operation
5~45 DEG C of temperature, export operation 0.25~0.55MPa of pressure, 25~65 DEG C of operation temperature；Coupler reactor (104) is tubulation
Formula fixed bed reactors, using load type palladium catalyst, palladium load quality content is 0.50%~3.50%, aluminium oxide Al 2O3
Carrier, 0.15~0.45MPa of operating pressure, 100~140 DEG C of operation temperature, carbon monoxide: mass ratio=1.0 of oxygen~
5.5:1；Oxalate recovery tower (105) 0.10~0.60MPa of operating pressure, 40~115 DEG C of tower top operation temperature, tower reactor operation temperature
95~145 DEG C of degree, reflux ratio 0.5~4.5；Oxalate product tower (106) 0.005~0.035MPa of operating pressure, tower top operation
15~55 DEG C of temperature, 108~138 DEG C of tower reactor operation temperature, reflux ratio 0.3~3.5；Carbon ester lower pressure column (107) operating pressure
0.10~0.30MPa, 45~75 DEG C of tower top operation temperature, 70~110 DEG C of tower reactor operation temperature, reflux ratio 8.0~25.0；Carbon ester
Pressurizing tower (108) 0.70~1.10MPa of operating pressure, 130~145 DEG C of tower top operation temperature, tower reactor operation temperature 165~195
DEG C, reflux ratio 2.0~16.0.
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