CN106866363A - A kind of synthesis gas that maximizes prepares the system and method for ethylene glycol - Google Patents
A kind of synthesis gas that maximizes prepares the system and method for ethylene glycol Download PDFInfo
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- CN106866363A CN106866363A CN201710074075.8A CN201710074075A CN106866363A CN 106866363 A CN106866363 A CN 106866363A CN 201710074075 A CN201710074075 A CN 201710074075A CN 106866363 A CN106866363 A CN 106866363A
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- ethylene glycol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/04—Preparation of esters of nitrous acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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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
Abstract
The invention discloses the system and method that a kind of synthesis gas that maximizes prepares ethylene glycol, the gas vent of the methanol rectification scrubbing tower is connected to the gas feed of esterification column, heavy constituent is transported to the oxonation device after the reaction of the esterification column, the raffinate discharge of esterification column, the gas feed of the oxonation device connects the gas vent of the esterification column, the reacted heavy constituent of oxonation device is transported to methanol rectification scrubbing tower, the gas feed of the hydrogenation reactor is connected after the dimethyl oxalate heating vaporization of the discharging opening of the dimethyl oxalate rectifying column, the gas vent discharge of the hydrogenation reactor, the purifying ethylene glycol tower connects the discharging opening of ethylene glycol rectifier unit, the gas vent of the ethylene glycol rectifier unit is connected to esterification column, the waste liquid discharge of the ethylene glycol rectifier unit.Reduce device series number, reduce equipment number of units, reduce construction investment, reduce the generation of side reaction thing, reduce consumption.
Description
Technical field
The present invention relates to a kind of H2With the method for CO synthesis gas preparing ethylene glycols, more particularly to a kind of maximization synthesis gas
Prepare the system and method for ethylene glycol.
Background technology
The catalyst preparation of domestic and international synthesis gas preparing ethylene glycol process route, Process Design Package, engineering are implemented, technique behaviour
Make index etc. and gradually tended to ripe, but synthesis gas preparing ethylene glycol larger-scale unit, reduce construction investment, it is energy-saving, enter
There are problems in the aspects such as one step improve product quality.
The shell and tube oxonation device and hydrogenation reactor that have been carried out now limit the development of ethylene glycol maximization.
Existing shell and tube oxonation device present situation：Oxonation device in operation now and the design of having put into operation at present is pipe
Formula reactor, the production scale of the formicester of oxalic acid two is 5 × 104tDMO/a、7.5×104tDMO/a、10×104tDMO/a、12.5
×104tDMO/a、20×104TDMO/a, domestic single maximum formicester device (20 × 10 of oxalic acid two of set4TDMO/a reactor)
Specification has chosen φ 6000 × 17793, HUrge=8000 specification, problems are brought to aspects such as transport, installation, operations, are managed
Formula reactor has limited maximization developing steps.
The tubular reactor bed resistance for having put into operation in 0.12-0.15MPa, according to circulating flow rate 7025.2Nm3/tDMO、
Pressure 0.135MPa pressure drops are calculated, and often produce 1 ton of DMO to need the power consumption of circulator is 186.19KW.h/tDMO；
Water route causes top to move hot ability using forced circulation, and forced circulation multiplying power is general at 6-8 times, according to circulation times
Rate 8 is calculated, then the peripheral hot water folder vapour rate of upper catalyst agent pipe is in 12.5% (1/8 × 100%), upper catalyst agent pipe periphery water
Folder vapour rate is very high, causes upper catalyst agent Guan Yire abilities；
Oxonation is second order reaction, and reaction is concentrated mainly on catalyst tube top and reacts, bottom balanced action, and on
Portion water side folder vapour rate is high, and influence bed moves hot merit energy.Gas side heat transfer is to during water side, and gas side is straight with the △ t of water side
Influence heat-transfer effect is connect, under the premise of same Coefficient K, then △ t are smaller, then heat-transfer capability is poorer, that is to say, that tubular type
Reactor seems heat exchange area greatly, and plays and remove the heat exchange area that bed heat relies primarily on catalyst tube top, and bottom
Because △ t diminish, beds heat is removed less；
When full factory has a power failure suddenly, water route is switched to Natural Circulation not in time, and because heat of reaction is gathered, beds surpass
Temperature, nitrous acid fat is thermally decomposed, and easily causes explosion accident, and this is also the main original that part producer oxonation explodes
Therefore one；
During the original filling of catalyst, being dropped by pressure measurement ensures that each catalyst tube resistance is identical, but hydrogenation or puts into operation one
After the section time, the catalyst in catalyst tube sinks highly and density is different, then each catalyst bed layer resistance is had any different,
Each beds tolerance certainly will be caused different, bring catalyst utilization to reduce；
Tubular reactor is difficult to eliminate the thermal stress between pipe and housing, the maximum oxonation device (φ of domestic separate unit
6000 × 17793 reactors, catalyst bed layer height reaches 8000mm), initial stage driving and parking fluctuation is larger, because stress problem is caused
Oxonation device is revealed；
Part new equipment, because personnel are inadequate to nitrous acid fat thermal decomposition understanding in oxonation, Catalyst packing and pipe
Plate upper surface is concordant, during initial stage test run, the sour fat thermal decomposition of pressure occurs, and tube sheet is burnt, is forced to change new reactor；
At present in 50 × 10 for building4The oxonation of tEG/a is constituted for 2 series, tubular type oxonation devices by 8, no
Only floor space is big, construction costs is high, easily causes gas bias current, and operation difficulty is big.
Existing shell and tube hydrogenation reactor present situation：During hydrogenation catalyst pilot scale, the selection of hydrogenation reactor catalyst heat exchange pipe
φ 25 or the specifications of φ 32.When implementing industrialized unit, software packet technology business is in order to realize that loaded catalyst is big and bed resistance
, be amplified to catalyst tube between 45~φ of φ 70 by low target, although being met from the catalyst heat exchange pipe of Large Diameter Pipeline
The purpose that loaded catalyst is big and bed resistance is low, but bring is that hydrogen ester is bigger than high, internal circulating load, tube wall temperature low (portion
There is " cold-wall effect " in divided catalyst), operation energy consumption certainly will be caused high, it is low that catalyst goes out power rate, and engineering is difficult to maximize etc. lacks
Point.Shell and tube hydrogenation reactor in having put into operation and designed at present is tubular reactor, separate unit ethylene glycol reactor production rule
Mould is 2.5 × 104tEG/a、5×104tEG/a、10×104TEG/a, most of 10 × 104TEG/a scales ethylene glycol hydrogenation dress
Put using two or more shell and tube hydrogenation reactor parallel running.The country only a set of 10 × 104TEG/a ethylene glycol hydrogenation plants
Hydrogenation reactor is separate unit, and specification has chosen φ 6800, and catalyst tube highly reaches 10000mm, to sides such as transport, installation, operations
Problems are brought in face, cannot be run because catalyst bed layer resistance is excessive, cause the fixed assets of investment tens to leave unused, tubular type
Reactor has limited complete preparing synthetic gas preparing ethylene glycol maximization developing steps.
At present in 50 × 10 for building4The hydrogenation reaction of tEG/a is constituted for 2 series, shell and tube hydrogenation reactors by 8,
4 parallel connections of single series are taken, due to the easy coking of hydrogenation reaction and the easy efflorescence of catalyst, is caused each in reactor and reactor
Catalyst tube resistance is different, then gas bias current occurs, beds local overheating, side reaction thing are high, catalyst utilization
It is low, the phenomenon such as rectifying separation circuit steam consumption is high and operation difficulty is big；
The tubular type hydrogenation reactor bed resistance for having put into operation in 0.25-0.35MPa, according to circulating flow rate 30438.8Nm3/
TEG, pressure 0.30MPa pressure drops are calculated, and often produce 1 ton of EG to need the power consumption of circulator is 132.98KW.h/tEG；
Water route causes top to move hot ability using forced circulation, and forced circulation multiplying power is general at 6-8 times, according to circulation times
Rate 8 is calculated, then the peripheral hot water folder vapour rate of upper catalyst agent pipe is in 12.5% (1/8 × 100%), upper catalyst agent pipe periphery water
Folder vapour rate is very high, causes upper catalyst agent Guan Yire abilities；
When full factory has a power failure suddenly, water route is switched to Natural Circulation not in time, and heat of reaction is gathered, beds overtemperature,
Easily cause beds coking, further larger catalyst bed resistance.
Device series number present situation：The domestic maximum glycol unit that put into operation is 30 × 104TEG/a, and actual is three set 20
×104TDMO/a carbonylations series (single set oxonation device is two DN4600 shell and tube reactors in parallel), three set 10 ×
104TEG/a hydrogenation series (single set hydrogenation reactor is two DN4200 shell and tube reactors in parallel), two set 15 × 104tEG/a
Rectifying separator.Floor space is big, to the soil of little waste more than 60%.It is secondary because carbonylation, hydrogenation catalyst bed temperature are high
Reactant is more, and ethylene glycol rectifying separator steam consumption is up to 9~11t/tEG.
Put into operation 20 × 10 in the country4TEG/a glycol units are two set 20 × 104TDMO/a carbonylations series (single set carbonylation
Reactor is two DN4600 shell and tube reactors in parallel), two set 10 × 104(list covers hydrogenation reactor to tEG/a hydrogenation series
Two DN4200 shell and tube reactors are in parallel), two set 10 × 104TEG/a rectifying separators.
Domestic and international synthesis gas preparing ethylene glycol device does not realize larger-scale unit truly, and device series number is more, work
Journey investment is big, management difficulty is big, operation energy consumption is high, operating cost is high, ethylene glycol product qualification rate is low, it is impossible to enough to replace stone completely
The ethylene glycol of oil circuit line.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of maximization synthesis gas prepares ethylene glycol
System and method, realizes that the maximization of low energy consumption prepares ethylene glycol.
The present invention is achieved by the following technical solutions, and what a kind of synthesis gas that maximizes of the present invention prepared ethylene glycol is
System, including esterification column, oxonation device, methanol rectification scrubbing tower, dimethyl oxalate rectifying column, hydrogenation reactor, ethylene glycol essence
Distillation unit, purifying ethylene glycol tower；The gas vent of the methanol rectification scrubbing tower is connected to the gas feed of esterification column, the ester
Heavy constituent is transported to the oxonation device, the raffinate discharge of esterification column, the gas of the oxonation device after changing the reaction of tower
Import connects the gas vent of the esterification column, and the gas feed of the methanol rectification scrubbing tower connects the gas of oxonation device
Outlet, the reacted heavy constituent of oxonation device is transported to methanol rectification scrubbing tower, the methanol rectification scrubbing tower reaction
Heavy constituent afterwards is transported to dimethyl oxalate rectifying column, the dimethyl oxalate heating of the discharging opening of the dimethyl oxalate rectifying column
The gas feed of the hydrogenation reactor is connected after vaporization, the discharging opening of the hydrogenation reactor connects ethylene glycol rectifier unit,
The gas vent discharge of the hydrogenation reactor, the purifying ethylene glycol tower connects the discharging opening of ethylene glycol rectifier unit, described
The gas vent of ethylene glycol rectifier unit is connected to esterification column, the waste liquid discharge of the ethylene glycol rectifier unit.
The system also includes liquid waste treating apparatus and exhaust gas processing device, the gas feed connection waste liquid of the esterification column
The gas vent of processing unit, the raffinate of esterification column enters liquid waste treating apparatus, and the discharging of waste liquid of ethylene glycol rectifier unit is to useless
Liquid processing device, a gas vent part for methanol rectification scrubbing tower is connected to liquid waste treating apparatus, the hydrogenation reactor
Gas vent is connected to exhaust gas processing device, the discharging of waste liquid of the ethylene glycol rectifier unit to liquid waste treating apparatus.At waste liquid
Reason device and exhaust gas processing device are all the aided processes of glycol unit.
The ethylene glycol rectifier unit is returned including eparating methanol tower, lightness-removing column, de-ethanol tower, ethylene glycol rectifying column and ethylene glycol
Receive tower；The material inlet of the eparating methanol tower connects the discharging opening of hydrogenation reactor, and the material inlet connection of the lightness-removing column is de-
The kettle material outlet of methanol column, the material inlet of the kettle material outlet connection de-ethanol tower of the lightness-removing column carries out decompression steaming
Evaporate, the kettle material outlet connection ethylene glycol rectifying column of the de-ethanol tower, the kettle material outlet of the ethylene glycol rectifying column
Ethylene glycol is obtained, the tower top material outlet of the ethylene glycol rectifying column and the tower top material outlet of de-ethanol tower connect second two respectively
Alcohol recovery tower.
A kind of method for preparing ethylene glycol, comprises the following steps：
(1) esterification step：Methyl alcohol and nitric oxide, the reaction generation nitrous acid fat of oxygen；
(2) carbonylation operation：The nitrous acid fat for obtaining will be reacted the generation formicester of oxalic acid two and carbon are coupled with carbon monoxide
Sour two formicesters；
(3) carbonylation gas separation circuit：By the formicester of oxalic acid two, dimethyl carbonate and nitrous acid formicester, carbon monoxide, nitrogen
Gas, nitric oxide, oxygen rectifying are separated；
(4) the formicester separation circuit of oxalic acid two：The formicester of oxalic acid two and dimethyl carbonate are completed into rectifying again to separate；
(5) hydrogenation process：By the formicester of oxalic acid two and hydrogen reaction generation ethylene glycol, methyl alcohol, ethanol, 1.2- butanediols, second
Alkyd methyl esters；
(6) ethylene glycol rectification working process：Ethylene glycol is completed into rectifying to separate；
(7) purifying ethylene glycol operation：Trace impurity in ethylene glycol is further converted to ethylene glycol or removing again, second is improved
Glycol purity, obtains high-purity ethylene glycol.
Methods described is further comprising the steps of：
(8) liquid waste processing operation：The raffinate of esterification is processed using nitric acid and nitric oxide reaction generation nitrogen dioxide,
Nitric acid mass content is less than 0.1% in making waste water；
(9) vent gas treatment operation：The waste gas in reaction is collected, heat resolve reaches discharge standard.
In the esterification step, the portion gas and oxygen mix of the discharge of carbonylation gas separation circuit enter esterification work
Sequence, the gas after the treatment of nitrate reductase operation is reacted also into esterification step with methyl alcohol, generates nitrous acid fat, raffinate row
Enter nitrate reductase operation.
In the carbonylation operation, the gas of esterification step discharge is reacted into carbonylation operation with nitrous acid fat, is generated
The formicester of oxalic acid two and dimethyl carbonate, the gas part for reacting discharge enter carbonylation gas separation circuit, partly into tail gas
Treatment process.
In the carbonylation gas separation circuit, the discharge gas of oxonation reacts into carbonylation gas separation circuit
Afterwards, using the formicester of oxalic acid two, dimethyl carbonate as heavy constituent realize rectifying separate, by nitrous acid formicester, carbon monoxide, nitrogen,
Nitric oxide, oxygen are discharged as light component, and the light component part enters esterification step, partly into nitrate reductase operation.
In the formicester separation circuit of the oxalic acid two, the formicester of oxalic acid two and dimethyl carbonate are separated, dimethyl carbonate conduct
Accessory substance is discharged, dimethyl oxalate feeding hydrogenation process；In the hydrogenation process, dimethyl oxalate heating vaporization is input to hydrogenation
Operation is discharged to tail with hydrogen reaction generation ethylene glycol, methyl alcohol, ethanol, 1.2- butanediols, methyl glycollate, reacted gas
Gas disposal operation, product delivers to ethylene glycol rectification working process.
In the ethylene glycol rectification working process, thick ethylene glycol is made qualified ethylene glycol product and purifying ethylene glycol operation is sent into
Refined, while gas is entered into esterification step, waste liquid is entered into nitrate reductase operation.
The present invention has advantages below compared to existing technology：
(1) present invention it is main by using coil pipe type oxonation device, coil pipe type hydrogenation reactor, nitrate reductase technology,
Filler realizes that glycol unit maximizes with the distillation tower technology of catalyst, reduces device series number, reduces equipment number of units, reduces
Construction investment, reduces the generation of side reaction thing, reduces operation energy consumption, reduces raw materials consumption；
(2)20×104TEG/a glycol unit abilities, esterification, carbonylation, hydrogenation, rectifying separation, nitrate reductase, ethylene glycol
Refined and tail gas recycle operation is capable of achieving single series, single device, and floor space at least saves more than 50%, construction investment drop
Low by more than 40%, operational administrative personnel reduce more than 40%, and synthesis gas is truly realized in operation energy consumption reduction by more than 30%
Preparing ethylene glycol larger-scale unit；
(3) coil pipe type oxonation device reaction bed temperature is " isothermal bed ", and bed temperature≤135 DEG C are shut out completely
There are pyrolysis in exhausted methyl nitrite, effectively improve the formicester of oxalic acid two, dimethyl carbonate yield, it is ensured that ethylene glycol product is excellent
More than 99.8% is reached Deng product, oxonation system operatio security is effectively improved, it is to avoid because of the explosion accident that thermal decomposition causes
Occur；
(4) coil pipe type hydrogenation reactor reaction bed temperature is " isothermal bed ", and bed temperature≤188 DEG C reduce grass
Sour two formicester excessive hydrogenations reaction and carburetting reaction, reduce ethanol, 1.2- butanediols, the generation of methyl glycollate side reaction thing, drop
Low ethylene glycol rectifying separate vapour consumption, while avoiding hydrogenation reactor from coking phenomenon occur, effectively extension catalyst uses the longevity
Life and processing safety；
(5) oxonation device and reinforcement reactor use coil pipe type radial gas distribution technique, only carbonylation, hydrogenation reaction
It is more than 400KW.h/tEG that the resistance of device reduction can reduce carbonylation and hydrogenation circulator power consumption；
(6) ethylene glycol is further refined using catalyst distillation technology, methyl alcohol is carried out using to gas after oxonation
Washing distillation technology, reduces side reaction thing and generates using serpentine reactor, the skill such as ethylene glycol rectifier unit heat energy staged is utilized
Art, the total steam consumption≤4.5t/tEG of synthesis gas preparing ethylene glycol maximization device of the invention, than the second two for having put into operation
Alcohol device ethylene glycol per ton at least saves 4.5~more than 6.5t/tEG of steam consumption；
(7) exclude the nitric acid in raffinate to esterification column using nitrate reductase technology to recycle, the discharge of nitrate reductase tower
Nitric acid content is reduced to less than 0.1% by original 0.5~1.5% in waste water, effectively reduces nitric acid, NaOH raw material and disappears
Consumption, while realizing discharged wastewater met the national standard, even more of esterification generation methyl nitrite supplements, and synthesis gas preparing ethylene glycol is big
Type makeup is put and takes nitrate reductase technology to achieve many things at one stroke；
(8) to the system heat energy of esterification step, carbonylation operation, hydrogenation process, rectifying separation circuit and nitrate reductase operation
All take staged to utilize, effectively reduce cooling-water consumption, cooling-water consumption is than traditional glycol unit reduction 150t/tEG
More than (containing chilled brine consumption)；
(9) synthesis gas preparing ethylene glycol of the invention maximizes technology from reducing operation energy consumption, reduce administration fee and reduction
Financial cost all aspect, ethylene glycol integrated cost valency in 3100 yuan/tEG or so, at least than existing glycol unit integrated cost
Reduce by 900 yuan/more than tEG；
(10) synthesis gas preparing ethylene glycol maximization technology of the invention solves synthesis gas preparing ethylene glycol maximization problem, if
Standby to be easy to amplify, each operation is under single series single device design conditions, ethylene glycol single series production capacity >=20 × 104tEG/
A, truly realizes the maximization of synthesis gas preparing ethylene glycol.
Brief description of the drawings
Fig. 1 is process chart of the invention；
Fig. 2 is the structural representation of esterification column；
Fig. 3 is the structural representation of coil pipe type oxonation device；
Fig. 4 is the structural representation of methanol rectification scrubbing tower；
Fig. 5 is the structural representation of dimethyl oxalate rectifying column；
Fig. 6 is the structural representation of coil pipe type hydrogenation reactor；
Fig. 7 is the structural representation of eparating methanol tower；
Fig. 8 is the structural representation of lightness-removing column；
Fig. 9 is the structural representation of de-ethanol tower；
Figure 10 is the structural representation of ethylene glycol rectifying column；
Figure 11 is the structural representation of ethylene glycol recovery tower；
Figure 12 is the structural representation of purifying ethylene glycol tower；
Figure 13 is the structural representation of nitrate reductase tower；
Figure 14 is the structural representation of tail gas recovery tower.
Specific embodiment
Embodiments of the invention are elaborated below, the present embodiment is carried out under premised on technical solution of the present invention
Implement, give detailed implementation method and specific operating process, but protection scope of the present invention is not limited to following implementations
Example.
As shown in figure 1, the present embodiment includes esterification step, carbonylation operation, carbonylation gas separation circuit, the formicester of oxalic acid two
Separation circuit, hydrogenation process, ethylene glycol rectification working process, purifying ethylene glycol operation, liquid waste processing operation, vent gas treatment operation, with
Upper each operation and capital equipment are single series separate unit, truly realize that synthesis gas preparing ethylene glycol maximizes.
The step of specifically preparing ethylene glycol is as follows：
(1) esterification step：Methyl alcohol is completed in esterification column with nitric oxide, the reaction generation nitrous acid fat of oxygen；
(2) carbonylation operation：The nitrous acid fat for obtaining will be reacted in oxonation device generation is coupled with carbon monoxide
The formicester of oxalic acid two and dimethyl carbonate；
(3) carbonylation gas separation circuit：By the formicester of oxalic acid two, dimethyl carbonate and nitrous in methanol rectification scrubbing tower
Sour formicester, carbon monoxide, nitrogen, nitric oxide, oxygen rectifying are separated；
(4) the formicester separation circuit of oxalic acid two：The formicester of oxalic acid two and dimethyl carbonate are completed in dimethyl oxalate rectifying column
Rectifying is separated；
(5) hydrogenation process：In hydrogenation reactor by the formicester of oxalic acid two and hydrogen reaction generation ethylene glycol, methyl alcohol, ethanol,
1.2- butanediols, methyl glycollate；
(6) ethylene glycol rectification working process：Returned by eparating methanol tower, lightness-removing column, de-ethanol tower, ethylene glycol rectifying column and ethylene glycol
Receive tower and complete ethylene glycol rectifying separation；
(7) purifying ethylene glycol operation：Trace impurity in ethylene glycol is further converted to second two in purifying ethylene glycol tower
Alcohol or removing, improve ethylene glycol purity, obtain high-purity ethylene glycol；
(8) liquid waste processing operation：Liquid waste processing operation includes nitrate reductase operation and wastewater treatment operation in waste liquid, utilizes
Nitric acid processes the raffinate of esterification with nitric oxide reaction generation nitrogen dioxide, and nitric acid content is less than 0.1%, drop in making waste water
Low nitric acid and NaOH consumption of raw materials, realize discharged wastewater met the national standard；
(9) vent gas treatment operation：The waste gas in reaction is collected, heat resolve reaches discharge standard.
As shown in Fig. 2 esterification column includes the esterification upper cover C2, esterification upper shell C6, the esterification centrum that set from top to bottom
C11, esterification lower shell C14, the top of esterification upper cover C2 set esterification column ejection material mouth C1, the bottom of esterification lower shell C14
Esterification tower reactor discharging opening C15 is set, and the top of esterification upper shell C6 sets the first esterification feed mouthful C3 and the second esterification feed mouthful
The bottom of C4, esterification upper shell C6 set the 3rd esterification feed mouthful C7, the 4th esterification feed mouthful C8, the 5th esterification charging aperture C9 and
6th esterification feed mouthful C10, filling esterification filler C5 in esterification upper shell C6, sets esterification column plate in esterification lower shell C14
C13。
Gas from the outlet of carbonylation gas separation circuit is divided to two strands, and one enters vent gas treatment operation, another stock
Into the 3rd esterification feed mouthful C7 and the O from the 4th esterification feed mouthful C8 of esterification column2From bottom to top through over-churning after mixing
Filler C5, the gas from nitrate reductase tower, also from bottom to top through over-churning filler C5, is being esterified by the 6th esterification feed mouthful C10
Filler C5 layers with the CH by the first esterification feed mouthful C3, the second esterification feed mouthful C43There is following reaction in OH：2NO+O2=2NO2、
NO+NO2=N2O3、2CH3OH+N2O3=2CH3ONO+H2O、CH3ONO+H2O=CH3OH+HNO2、2NO2=N2O4、N2O4+CH3OH
=CH3ONO+HNO3.Nitrous acid fat is that product required for esterification, generation product are extracted out from esterification column ejection material mouth C1, together
When with the compositions such as nitric acid, nitrous acid and water raffinate, raffinate extracts out from esterification tower reactor discharging opening C15.Esterification column selection esterification
Filler C5 coordinates the composite construction tower of esterification column plate C13, esterification filler C5 increases CH3OH and N2O3Contact area, completion heat transfer,
Effect of mass transmitting, while completing rectifying separates task, light component is extracted out from esterification column ejection material mouth C1, heavy constituent goes out from esterification tower reactor
Material mouth C15 is extracted out.Methyl alcohol, nitric acid in raffinate are further evaporated to C5 layers of esterification filler and participate in reaction by esterification column plate C13, enter one
Step reduces methyl alcohol, the content of nitric acid in raffinate.
As shown in figure 3, coil pipe type oxonation device includes that carbonylation pressure-bearing shell A9, carbonylation upper cover A5, carbonylation support are flat
The outer inflator A10 of straight tube header A7, carbonylation flat cover A6, carbonylation, carbonyl on platform A16, carbonylation low head A17, carbonylation outlet pipe A4, carbonylation
Inflator A12, carbonylation coiled pipe A11, carbonylation lower straighttube header A13, carbonylation branch pipe A14, carbonylation endless tube A15 and carbonylation water inlet pipe in changing
A18, the carbonylation outlet pipe A4 is connected to the top of carbonylation pressure-bearing shell A9, and straight tube header A7 connects carbonyl respectively on the carbonylation
The import of water pipe A4 and the outlet of carbonylation coiled pipe A11 are dissolved, the carbonylation coiled pipe A11 divides along the axial direction of carbonylation pressure-bearing shell A9
Cloth, the import that the carbonylation coiled pipe A11 is connected respectively and the outlet of carbonylation branch pipe A14 of the carbonylation lower straighttube header A13, institute
The bottom that water inlet pipe is connected to carbonylation pressure-bearing shell A9 is stated, the carbonylation endless tube A15 connects carbonylation water inlet pipe A18 and carbonylation respectively
Branch pipe A14；Straight tube header A7 is identical with carbonylation lower straighttube header A13 structures on the carbonylation, respectively including along carbonylation pressure-bearing shell
Multiple connecting tubes that body A9 is radially angularly set, the connecting tube is vertically set on the cross section of the carbonylation pressure-bearing shell A9
On, one end connection carbonylation coiled pipe A11 of the connecting tube, the other end connects corresponding pipeline；The carbonylation upper cover A5 and shell
Body is connected by carbonylation flange A8, and the carbonylation support platform A16 is arranged on carbonylation low head A17, the carbonylation low head
A17 is fixed on the bottom of housing；The carbonylation upper cover A5 is provided with carbonylation thermocouple port A1, carbonylation water outlet A 2 and carbonylation
Gas port A3, the carbonylation outlet pipe A4 are arranged in carbonylation water outlet A 2；The carbonylation low head A17 is provided with gas port under carbonylation
A20, carbonylation water inlet A 19 and carbonylation catalyst self-unloading mouthful A21；The carbonylation water inlet pipe A18 is arranged on carbonylation water inlet A 19
It is interior；The carbonylation flat cover A6 is arranged on the top of straight tube header A7 on carbonylation, and the outer inflator A10 of the carbonylation is along carbonylation pressure-bearing shell
A9's is axially arranged, and inflator A12 is set in the outer inflator A10 of carbonylation in the carbonylation, and the carbonylation coiled pipe A11 is arranged at carbonylation
In space in outer inflator A10 and carbonylation between inflator A12, the carbonylation is outer to be had between inflator A10 and carbonylation pressure-bearing shell A9
Have space, on the carbonylation straight tube header A7 and carbonylation lower straighttube header A13 be separately positioned on the outer inflator A10 of carbonylation top and
Bottom, the carbonylation lower straighttube header A13 is supported on carbonylation support platform A16, the carbonylation outlet pipe A4, carbonylation flat cover
Inflator A12, carbonylation lower straighttube header in the outer inflator A10 of straight tube header A7, carbonylation, carbonylation coiled pipe A11, carbonylation on A6, carbonylation
Loading catalyst in the space that A13, carbonylation branch pipe A14, carbonylation endless tube A15, carbonylation water inlet pipe A18 are formed.
The gas of the esterification column ejection material mouth C1 from esterification column is by entering coil pipe type oxonation after molecular sieve drying
Device, inflator A12 in carbonylation is entered by gas port A20 under carbonylation, is evenly distributed to beds by inflator A12 in carbonylation, instead
Heat should be released and be embedded in the carbonylation coiled pipe A11 internal water absorptions of beds inside, be eventually converted into steam and take catalyst out of
Bed, reacted gas is collected by the outer inflator A10 of carbonylation, finally goes out oxonation device by gas port A3 on carbonylation.In palladium system
Under catalyst existence condition, the main nitrous acid fat that completes couples the generation formicester of oxalic acid two with CO in coil pipe type oxonation device
And dimethyl carbonate, key reaction is as follows：2CH3ONO+2CO=CH3OCOCOCH3O+2NO、2CH3ONO+CO=CH3OCOCH3O+
2NO、2CH3ONO=HCHO+CH3OH+2NO.Product dimethyl carbonate is added value side reaction thing higher, product oxalic acid diformazan
Fat is the intermediate of ethylene glycol product, formaldehyde be the side reaction thing of thermal decomposition, it is necessary to control the growing amount of formaldehyde, nitric oxide,
The light component such as nitrogen, remaining carbon monoxide, oxygen needs to recycle.Using maximization coil pipe reactor as oxonation
Device replaces existing shell and tube oxonation device.It is main heat-exchanging tube bundle to use carbonylation coiled pipe A11, and carbonylation coiled pipe A11 is restrained in axle
Thermal stress is eliminated to radially thorough.Ensure that gas is flowed radially across using inflator A12 technologies in the outer inflator A10 of carbonylation and carbonylation
Beds, gas flow direction is plumbness with water flow direction.Between being restrained using drum and carbonylation coiled pipe A11
Waterway circulating to follow naturally, and waterway circulating multiplying power is high；Realize that loaded catalyst is more, shifting heat energy power is strong, catalyst bed layer resistance
It is low, it is easy to which that glycol unit maximizes.
As shown in figure 4, methanol rectification scrubbing tower includes the methanol rectification upper cover E2, the methanol rectification cylinder that set from top to bottom
Body E6, methanol rectification low head E9；The top of methanol rectification upper cover E2 sets methanol rectifying tower ejection material mouth E1, methanol rectification
The bottom of low head E9 sets methanol rectification tower reactor discharging opening E10, and the top of methanol rectification cylinder E6 is provided with the first methanol rectification
The bottom of charging aperture E3 and the second methanol rectification charging aperture E4, methanol rectification cylinder E6 be provided with the 3rd methanol rectification charging aperture E7 and
Filling methanol rectification filler E5 in 4th methanol rectification charging aperture E8, methanol rectification cylinder E6.
The gas of gas port A3 enters maximization methanol rectification washing on carbonylation from maximization coil pipe type oxonation device
3rd methanol rectification charging aperture E7 of tower, from bottom to top into methanol rectification filler E5, with the first methanol rectification charging aperture E3 and
The methyl alcohol of the second methanol rectification charging aperture E4 completes washing and rectifying task, and light component and methanol rectifying tower ejection material mouth E1 are extracted out
After go circulator to be pressurized, enter subsequent cycle, dimethyl carbonate, oxalic acid two into large-scale esterification column and maximization nitrate reductase tower
The heavy constituents such as formicester are extracted out by methanol rectification tower reactor discharging opening E10 and enter maximization oxalic acid two formicester rectifying column completion carbonic acid diformazan
Fat is separated with the formicester rectifying of oxalic acid two.The formicester of oxalic acid two and dimethyl carbonate and nitrous are completed in maximization methanol rectification scrubbing tower
Sour methyl esters, CO, N2、NO、O2Rectifying separate, using methyl alcohol washing methods by the formicester of oxalic acid two of heavy constituent in carbonylation gas
And dimethyl carbonate is washed, extracted out by tower reactor.Methyl nitrite, CO, N2、NO、O2Etc. light component by tower top extract out, plus
Esterification step is re-fed into after pressure and participates in subsequent cycle reaction.
As shown in figure 5, the formicester rectifying column of oxalic acid two includes the formicester upper cover F2 of oxalic acid two, the oxalic acid two that set from top to bottom
Formicester cylinder F7, the formicester low head F9 of oxalic acid two；The top of the formicester upper cover F2 of oxalic acid two sets the discharging of the formicester tower top of oxalic acid two
The bottom of mouth F1, the formicester low head F9 of oxalic acid two sets the formicester tower reactor discharging opening F10 of oxalic acid two, and the formicester cylinder F7's of oxalic acid two is upper
Portion is provided with the formicester charging aperture F3 of the first oxalic acid two and formicester charging aperture F4 of the second oxalic acid two, is set in the middle part of the formicester cylinder F7 of oxalic acid two
The bottom for having the formicester charging aperture F5 of the 3rd oxalic acid two, the formicester cylinder F7 of oxalic acid two is provided with the formicester charging aperture F8 of the 4th oxalic acid two, grass
Filling oxalic acid two formicester filler F6 in two formicester cylinder F7 of acid.
The material of the methanol rectification tower reactor discharging opening E10 from maximization methanol rectification scrubbing tower enters maximization oxalic acid two
The formicester charging aperture F5 of 3rd oxalic acid two of formicester rectifying column, enters with the formicester charging aperture F3 of the first oxalic acid two with the formicester of the second oxalic acid two
The material of material mouth F4, completes rectifying and separates task in the formicester filler F6 of oxalic acid two.Grass is completed in maximization oxalic acid diformazan rectifying column
Sour two formicesters are separated with dimethyl carbonate rectifying, and dimethyl carbonate is sent to as added value accessory substance higher, the formicester of oxalic acid two
Hydrogenation process further reacts, and dimethyl carbonate is that light component is extracted out from the formicester tower top discharging opening F1 of oxalic acid two, the formicester of oxalic acid two
For heavy constituent is extracted out from the formicester tower reactor discharging opening F10 of oxalic acid two.
As shown in fig. 6, the structure of coil pipe type hydrogenation reactor is identical with oxonation device, enter the in opposite direction of outlet.Come
Pass through heating vaporization, power from the formicester of oxalic acid two of the formicester tower reactor discharging opening F10 of oxalic acid two of maximization oxalic acid diformazan rectifying column
Gas port B3 on the hydrogenation of maximization coil pipe type hydrogenation reactor is transported to, the outer inflator B10 of hydrogenation, warp are entered by the upper gas port B3 of hydrogenation
Cross the outer inflator B10 of hydrogenation and be evenly distributed to beds, reaction is released heat and is embedded in beds inside hydrogenation coiled pipe
B11 internal waters are absorbed, and are eventually converted into steam and take beds out of, and reacted gas is collected by inflator B12 in hydrogenation,
It is final that the hydrogenation reactor that maximizes is gone out by the lower gas port B20 of hydrogenation.Under copper silicon systems catalyst existence condition, completed in hydrogenation reactor
The formicester of oxalic acid two and H2Reaction generation ethylene glycol and methyl alcohol, ethanol, 1.2- butanediols, methyl glycollate, key reaction：
CH3OCOCOCH3O+2H2=HOCH2COOCH3+CH3OH、HOCH2COOCH3+2H2=HOCH2CH2OH+CH3OH、HOCH2CH2OH+
H2=CH3CH2OH+H2O、HOCH2CH2OH+CH3CH2OH=HOCH2C(CH2CH3)HOH+H2O.Ethylene glycol is final products, second
Alcohol, 1.2- butanediols, methyl glycollate are added value byproduct higher, and methyl alcohol can be recycled；Reacted using coil pipe type
Device replaces existing shell and tube hydrogenation reactor as hydrogenation reactor, coil pipe type hydrogenation reactor include hydrogenation pressure-bearing shell B9,
Catalyst framework and heat-exchanging tube bundle, catalyst framework and heat-exchanging tube bundle are separately positioned in hydrogenation pressure-bearing shell B9.Using hydrogenation
Coiled pipe B11 is main heat-exchanging tube bundle, and thoroughly elimination thermal stress is axially and radially being gone up in hydrogenation coiled pipe B11 tube banks.It is outer using hydrogenation
Inflator B12 technologies ensure that gas flows radially across beds, gas flow direction and water flow direction in inflator B10 and hydrogenation
It is plumbness.Use the waterway circulating between drum and the A11B11 tube banks of hydrogenation coiled pipe to follow naturally, waterway circulating multiplying power is high,
Loaded catalyst is more, strong, catalyst bed layer resistance is low to move heat energy power, it is easy to which glycol unit maximizes.
As shown in Fig. 7~11, the thick ethylene glycol from hydrogenation process enters ethylene glycol rectifying separation circuit, ethylene glycol rectifying
Separation circuit completes ethylene glycol rectifying by eparating methanol tower, lightness-removing column, de-ethanol tower, ethylene glycol rectifying column and ethylene glycol recovery tower
Separation task.
As shown in fig. 7, eparating methanol tower includes the separating methanol upper cover G2, separating methanol cylinder G6, the piptonychia that set from top to bottom
Alcohol low head G8；The top of separating methanol upper cover G2 sets eparating methanol tower ejection material mouth G1, and the bottom of separating methanol low head G8 sets
The top for putting separating methanol tower reactor discharging opening G9, separating methanol cylinder G6 is provided with the first separating methanol charging aperture G3, separating methanol cylinder G6's
Middle part is provided with the second separating methanol charging aperture G5, and the bottom of separating methanol cylinder G6 is provided with the 3rd separating methanol charging aperture G7, separating methanol cylinder
Filling separating methanol filler G4 in body G6.
As shown in figure 8, lightness-removing column includes the de- light upper cover H2 for setting from top to bottom, takes off light cylinder H6, takes off light low head
H8；The top for taking off light upper cover H2 sets lightness-removing column ejection material mouth H1, and the bottom for taking off light low head H8 sets the discharging of lightness-removing column kettle
Mouth H9, the top for taking off light cylinder H6 is provided with the first de- light charging aperture H3, takes off and be provided with the middle part of light cylinder H6 the second de- light charging aperture
H5, the bottom for taking off light cylinder H6 is provided with the 3rd de- light charging aperture H7, takes off the de- lightweight filler H4 of filling in light cylinder H6.
As shown in figure 9, de-ethanol tower includes the de- ethanol upper cover I2, de- ethanol cylinder I7, the de- second that set from top to bottom
Alcohol low head I9；The top of de- ethanol upper cover I2 sets de-ethanol tower ejection material mouth I1, and the bottom of de- ethanol low head I9 sets
De-ethanol tower kettle discharging opening I10 is put, the top of de- ethanol cylinder I7 is provided with the first de- de- ethanol of ethanol charging aperture I3 and second and enters
Material mouth I4, is provided with the 3rd de- ethanol charging aperture I6 in the middle part of de- ethanol cylinder I7, the bottom of de- ethanol cylinder I7 is provided with the 4th and takes off
Ethanol charging aperture I8, takes off the de- ethanol filler I5 of filling in ethanol cylinder I7.
As shown in Figure 10, ethylene glycol rectifying column includes the ethylene glycol rectifying upper cover J2, the ethylene glycol essence that set from top to bottom
Evaporate cylinder J6, ethylene glycol rectifying low head J8；The top of ethylene glycol rectifying upper cover J2 sets ethylene glycol rectifying tower top discharging opening
The bottom of J1, ethylene glycol rectifying low head J8 sets ethylene glycol rectifying tower reactor discharging opening J9, the top of ethylene glycol rectifying cylinder J6
The first ethylene glycol rectifying charging aperture J3 is provided with, the second ethylene glycol rectifying charging aperture J5 is provided with the middle part of ethylene glycol rectifying cylinder J6,
The bottom of ethylene glycol rectifying cylinder J6 is provided with filling ethylene glycol in triethylene glycol rectifying charging aperture J7, ethylene glycol rectifying cylinder J6
Fractional distillation filling-material J4.
As shown in figure 11, ethylene glycol recovery tower includes that the ethylene glycol for setting from top to bottom reclaims upper cover K2, ethylene glycol and returns
Receive cylinder K6, ethylene glycol and reclaim low head K8；The top that ethylene glycol reclaims upper cover K2 sets ethylene glycol recovery tower ejection material mouth
K1, the bottom that ethylene glycol reclaims low head K8 sets ethylene glycol recovery tower reactor discharging opening K9, and ethylene glycol reclaims the cylinder of cylinder K6
It is provided with the first ethylene glycol and reclaims charging aperture K4 and the second ethylene glycol recovery charging aperture K5, the bottom that ethylene glycol reclaims cylinder K6 is provided with
Triethylene glycol reclaims charging aperture K7, and ethylene glycol reclaims filling ethylene glycol in cylinder K6 and reclaims filler K3.
Eparating methanol tower is atmospheric distillation, mainly removes the methyl alcohol in thick ethylene glycol, and Methanol Recovery is recycled, light component methyl alcohol
Extracted out from eparating methanol tower ejection material mouth G1, heavy constituent is extracted out from separating methanol tower reactor discharging opening G9.
Lightness-removing column is rectification under vacuum, lightness-removing column ejection material mouth H1 extraction light impurities, ethanol, water, dimethyl oxalate, glycolic
Methyl esters and formaldehyde, lightness-removing column kettle discharging opening H9 outlets, obtain ethylene glycol crude product (ethylene glycol and 1,2- butanediol, ethanol etc.).
De-ethanol tower is rectification under vacuum, and lightness-removing column kettle material carries out rectification under vacuum, de-ethanol tower top into de-ethanol tower
Discharging opening I1 extraction light component materials deliver to ethylene glycol recovery tower recovery section ethylene glycol, and de-ethanol tower kettle discharging opening I10 is obtained
Ethylene glycol crude product enters ethylene glycol rectifying column rectification under vacuum, and ethylene glycol rectifying tower reactor discharging opening J9 obtains qualified ethylene glycol and produces
Product (mass fraction is more than or equal to 99.8%).The tower top of de-ethanol tower ejection material mouth I1 and ethylene glycol rectifying tower top discharging opening J1 is adopted
Go out light component into ethylene glycol recovery tower, reclaim useful material.
As shown in figure 12, purifying ethylene glycol tower includes the purifying ethylene glycol upper cover L2, the ethylene glycol essence that set from top to bottom
Cylinder L5 processed, purifying ethylene glycol low head L6；The top of purifying ethylene glycol upper cover L2 sets purifying ethylene glycol tower top discharging opening
The bottom of L1, purifying ethylene glycol low head L6 sets purifying ethylene glycol tower reactor discharging opening L7, the cylinder of purifying ethylene glycol cylinder L5
It is provided with filling purifying ethylene glycol catalyst L4 in purifying ethylene glycol charging aperture L3, purifying ethylene glycol cylinder L5.
Micro aldehyde, ketone, fat in ethylene glycol are further converted to ethylene glycol or removing in purifying ethylene glycol tower, second two is improved
Alcohol purity, using catalytic distillation principle, different towers is placed on by the acid resin catalyst of aldehyde, ketone, fat difference catalytic performance
On plate, purifying ethylene glycol catalyst L4 is acid resin catalyst, be catalyst be again rectifying separate heat and mass filler,
Quality of ethylene glycol product is further improved so as to reach, ethylene glycol enters from purifying ethylene glycol charging aperture L3, from purifying ethylene glycol
Tower reactor discharging opening L7 further refined after ethylene glycol product.
As shown in figure 13, liquid waste treating apparatus are nitrate reductase tower, and nitrate reductase tower is used as the nitrate reductase operation of waste liquid,
Nitrate reductase tower includes the nitrate reductase upper cover D2, nitrate reductase upper shell D7, the nitrate reductase centrum that set from top to bottom
D10, nitrate reductase lower shell D11 and nitrate reductase low head D13, the top of nitrate reductase upper cover D2 set nitrate reductase tower
The bottom of ejection material mouth D1, nitrate reductase low head D13 sets nitrate reductase tower reactor discharging opening D14, nitrate reductase upper shell D7
Top set the first nitrate reductase charging aperture D3 and the second nitrate reductase charging aperture D4, set in the middle part of nitrate reductase upper shell D7
The 3rd nitrate reductase charging aperture D8 is put, the bottom of nitrate reductase upper shell D7 sets the 4th nitrate reductase charging aperture D9, and nitric acid is also
Alternately filling nitrate reductase filler D5 and nitrate reductase catalyst D6, nitrate reductase lower shell D11 is interior in former upper shell D7 is set
Nitrate reductase column plate D12.
Nitric acid is completed in nitrate reductase tower with NO reaction generations NO2, nitric acid content is less than 0.1% in reducing waste water, reduces
Nitric acid and NaOH consumption of raw materials, realize discharged wastewater met the national standard, and key reaction is as follows：NO+0.5O2=NO2、2HNO3+ NO=
2NO2+H2O、NO+NO2=N2O3、2CH3OH+N2O3=2CH3ONO+H2O.Nitrate reductase operation is a treatment ester of ethylene glycol
An environmentally friendly operation of nitric acid is carried in change reaction waste secretly, while be again one being mended toward esterification supplement NO and past oxonation
The operation of nitrous acid fat is filled, nitric acid, NaOH consumption of raw materials is not only reduced, while discharged wastewater met the national standard is realized, while being also
One supplement of esterification generation methyl nitrite.Main light component (the nitrous come using carbonylation gas separation circuit
Sour methyl esters, CO, N2、NO、O2) exclude raffinate (containing 0.5~1.5% nitric acid) reaction, light component (nitrous acid with esterification column tower reactor
Methyl esters, CO, N2、NO、O2) extracted out from tower top, heavy constituent (mainly H2O, wherein HNO3≤ 0.1%), heavy constituent is taken out from tower reactor
Go out, then carry out acid-base neutralization reaction, qualified discharge with NaOH (NaOH) again.
As shown in figure 14, exhaust gas processing device is tail gas recovery tower, for exhaust-gas treatment, including the tail for setting from top to bottom
Gas disposal upper cover M2, vent gas treatment housing M6, vent gas treatment low head M10, the inside of vent gas treatment housing M6 is provided with pipe
Plate M3 and lower perforated plate M9, is provided with multiple heat exchanger tube M5 be arrangeding in parallel, vent gas treatment housing between upper perforated plate M3 and lower perforated plate M9
It is provided with multiple deflection plate M7 in M6, deflection plate M7 being radially arranged along multiple heat exchanger tube M5, vent gas treatment upper cover M2's
Top is provided with the first vent gas treatment discharging opening M1, and the top of vent gas treatment housing M6 is provided with the second vent gas treatment discharging opening M4, tail
The bottom of gas disposal low head M10 is provided with the first vent gas treatment charging aperture M11, and the bottom of vent gas treatment housing M6 is provided with the second tail
Gas disposal charging aperture M8.
Vent gas treatment operation is mainly by nitrous acid fat (CH in waste gas3ONO) pernicious gas heat resolve, reaches environment protection emission
Or send the boiler combustion, key reaction to be：2CH3ONO=HCHO+CH3OH+2NO., at 140 DEG C, 220 DEG C can be completely for nitrous acid fat
Decompose, it is 3216j/gMN that pyrolysis occur to release heat, releases heat to thermal decomposition and takes byproduct steam mode to reclaim.
Maximization of the invention is prepared the technique and traditional technics comparing of ethylene glycol, concrete outcome is as follows：
The present invention of table 1 sets contrast list with traditional ethylene glycol process sequence number
Note：1 ton of ethylene glycol (EG) of production needs the 2 tons of formicester of oxalic acid two (DMO)
The present invention of table 2 and traditional ethylene glycol technique main equipment selection contrast guide look
The present invention of table 3 and traditional ethylene glycol technique major economic indicators contrast guide look
The present invention of table 4 and traditional ethylene glycol construction investment contrast guide look
Presently preferred embodiments of the present invention is the foregoing is only, is not intended to limit the invention, it is all in essence of the invention
Any modification, equivalent and improvement made within god and principle etc., should be included within the scope of the present invention.
Claims (10)
1. the system that a kind of synthesis gas that maximizes prepares ethylene glycol, it is characterised in that including esterification column, oxonation device, methyl alcohol
Rectification washing tower, dimethyl oxalate rectifying column, hydrogenation reactor, ethylene glycol rectifier unit, purifying ethylene glycol tower；The methyl alcohol essence
The gas vent for evaporating scrubbing tower is connected to the gas feed of esterification column, and heavy constituent is transported to the carbonyl after the reaction of the esterification column
Change reactor, the raffinate discharge of esterification column, the gas feed of the oxonation device connects the gas vent of the esterification column, institute
The gas feed for stating methanol rectification scrubbing tower connects the gas vent of oxonation device, the reacted restructuring of oxonation device
Divide and be transported to methanol rectification scrubbing tower, the reacted heavy constituent of methanol rectification scrubbing tower is transported to dimethyl oxalate rectifying
Tower, connects the gas of the hydrogenation reactor after the dimethyl oxalate heating vaporization of the discharging opening of the dimethyl oxalate rectifying column
Import, the discharging opening connection ethylene glycol rectifier unit of the hydrogenation reactor, the gas vent discharge of the hydrogenation reactor, institute
The discharging opening that purifying ethylene glycol tower connects ethylene glycol rectifier unit is stated, the gas vent of the ethylene glycol rectifier unit is connected to ester
Change tower, the waste liquid discharge of the ethylene glycol rectifier unit.
2. the system that a kind of synthesis gas that maximizes according to claim 1 prepares ethylene glycol, it is characterised in that the system
Also include liquid waste treating apparatus and exhaust gas processing device, the gas of the gas feed connection liquid waste treating apparatus of the esterification column goes out
Mouthful, the raffinate of esterification column enters liquid waste treating apparatus, and the discharging of waste liquid of ethylene glycol rectifier unit is to liquid waste treating apparatus, and methyl alcohol is smart
The gas vent part for evaporating scrubbing tower is connected to liquid waste treating apparatus, and the gas vent of the hydrogenation reactor is connected to tail gas
Processing unit, the discharging of waste liquid of the ethylene glycol rectifier unit to liquid waste treating apparatus.
3. the system that a kind of synthesis gas that maximizes according to claim 1 prepares ethylene glycol, it is characterised in that the second two
Alcohol rectifier unit includes eparating methanol tower, lightness-removing column, de-ethanol tower, ethylene glycol rectifying column and ethylene glycol recovery tower；The separating methanol
The material inlet of tower connects the discharging opening of hydrogenation reactor, and the material inlet of the lightness-removing column connects the kettle material of eparating methanol tower
Outlet, the material inlet of the kettle material outlet connection de-ethanol tower of the lightness-removing column carries out vacuum distillation, the de-ethanol tower
Kettle material outlet connection ethylene glycol rectifying column, the ethylene glycol rectifying column kettle material outlet obtain ethylene glycol, it is described
The tower top material outlet of ethylene glycol rectifying column and the tower top material outlet of de-ethanol tower connect ethylene glycol recovery tower respectively.
4. a kind of method that system as claimed in claim 1 or 2 prepares ethylene glycol, it is characterised in that comprise the following steps：
(1) esterification step：Methyl alcohol and nitric oxide, the reaction generation nitrous acid fat of oxygen；
(2) carbonylation operation：The nitrous acid fat for obtaining will be reacted the generation formicester of oxalic acid two and carbonic acid two are coupled with carbon monoxide
Formicester；
(3) carbonylation gas separation circuit：By the formicester of oxalic acid two, dimethyl carbonate and nitrous acid formicester, carbon monoxide, nitrogen,
Nitric oxide, oxygen rectifying are separated；
(4) the formicester separation circuit of oxalic acid two：The formicester of oxalic acid two and dimethyl carbonate are completed into rectifying again to separate；
(5) hydrogenation process：By the formicester of oxalic acid two and hydrogen reaction generation ethylene glycol, methyl alcohol, ethanol, 1.2- butanediols, glycolic
Methyl esters；
(6) ethylene glycol rectification working process：Ethylene glycol is completed into rectifying to separate；
(7) purifying ethylene glycol operation：Trace impurity in ethylene glycol is further converted to ethylene glycol or removing again, ethylene glycol is improved
Purity, obtains high-purity ethylene glycol.
5. a kind of method for preparing ethylene glycol according to claim 4, it is characterised in that methods described also includes following step
Suddenly：
(8) liquid waste processing operation：The raffinate of esterification is processed using nitric acid and nitric oxide reaction generation nitrogen dioxide, makes to give up
Nitric acid mass content is less than 0.1% in water；
(9) vent gas treatment operation：The waste gas in reaction is collected, heat resolve reaches discharge standard.
6. a kind of method for preparing ethylene glycol according to claim 5, it is characterised in that in the esterification step, carbonylation is closed
Portion gas and oxygen mix into the discharge of gas separation circuit enter esterification step, and the gas after the treatment of nitrate reductase operation also enters
Enter esterification step, reacted with methyl alcohol, generate nitrous acid fat, raffinate enters nitrate reductase operation.
7. a kind of method for preparing ethylene glycol according to claim 5, it is characterised in that in the carbonylation operation, be esterified work
The gas of sequence discharge is reacted into carbonylation operation with nitrous acid fat, generates the formicester of oxalic acid two and dimethyl carbonate, reaction row
The gas part for going out enters carbonylation gas separation circuit, partly into vent gas treatment operation.
8. a kind of method for preparing ethylene glycol according to claim 5, it is characterised in that the carbonylation gas separation circuit
In, after the discharge gas of oxonation enters the reaction of carbonylation gas separation circuit, using the formicester of oxalic acid two, dimethyl carbonate as
Heavy constituent realizes that rectifying is separated, and nitrous acid formicester, carbon monoxide, nitrogen, nitric oxide, oxygen is discharged as light component, institute
State light component part and enter esterification step, partly into nitrate reductase operation.
9. a kind of method for preparing ethylene glycol according to claim 5, it is characterised in that the formicester separation circuit of the oxalic acid two
In, the formicester of oxalic acid two and dimethyl carbonate are separated, dimethyl carbonate is discharged as accessory substance, dimethyl oxalate feeding hydrogenation work
Sequence；In the hydrogenation process, dimethyl oxalate heating vaporization be input to hydrogenation process and hydrogen reaction generation ethylene glycol, methyl alcohol,
Ethanol, 1.2- butanediols, methyl glycollate, reacted gas are discharged to vent gas treatment operation, and product delivers to ethylene glycol
Rectification working process.
10. a kind of method for preparing ethylene glycol according to claim 5, it is characterised in that in the ethylene glycol rectification working process,
Thick ethylene glycol is made qualified ethylene glycol product and sends into purifying ethylene glycol operation and is refined, while gas is entered into esterification work
Sequence, nitrate reductase operation is entered by waste liquid.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734559A (en) * | 2019-03-05 | 2019-05-10 | 西南化工研究设计院有限公司 | The energy saving technique and system of nitrous acid ester regeneration by-product dust technology in ethylene glycol preparation |
| CN109942371A (en) * | 2019-03-20 | 2019-06-28 | 江苏凯美普瑞工程技术有限公司 | Staked type coal-ethylene glycol reaction unit and method |
| RU2719441C1 (en) * | 2018-10-22 | 2020-04-17 | Пуцзин Кемикал Индастри Ко., Лтд | Reactor for large-scale synthesis of ethylene glycol |
| WO2021089183A1 (en) * | 2019-11-05 | 2021-05-14 | Linde Gmbh | Process and plant for producing monoethylene glycol |
| CN113912491A (en) * | 2020-07-10 | 2022-01-11 | 中国石油化工股份有限公司 | Method and device for safely preparing dimethyl oxalate in coupling reactor and application of method and device |
| WO2022110871A1 (en) * | 2020-11-30 | 2022-06-02 | 南京延长反应技术研究院有限公司 | Enhanced micro-interface reaction system and method for preparing ethylene glycol by oxalate method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898311A (en) * | 2012-10-12 | 2013-01-30 | 上海焦化有限公司 | Method and equipment for continuously producing methyl nitrite |
| CN103483150A (en) * | 2013-08-31 | 2014-01-01 | 安徽淮化股份有限公司 | Method and device for producing and synthesizing ethylene glycol by using coal as raw material |
| CN104098441A (en) * | 2014-06-05 | 2014-10-15 | 上海戊正工程技术有限公司 | Technology and device system for producing dimethyl oxalate by high-pressure carbonylation of industrial synthesis gases and producing ethylene glycol through dimethyl oxalate hydrogenation |
-
2017
- 2017-02-10 CN CN201710074075.8A patent/CN106866363B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898311A (en) * | 2012-10-12 | 2013-01-30 | 上海焦化有限公司 | Method and equipment for continuously producing methyl nitrite |
| CN103483150A (en) * | 2013-08-31 | 2014-01-01 | 安徽淮化股份有限公司 | Method and device for producing and synthesizing ethylene glycol by using coal as raw material |
| CN104098441A (en) * | 2014-06-05 | 2014-10-15 | 上海戊正工程技术有限公司 | Technology and device system for producing dimethyl oxalate by high-pressure carbonylation of industrial synthesis gases and producing ethylene glycol through dimethyl oxalate hydrogenation |
Non-Patent Citations (1)
| Title |
|---|
| 冯再南等: "《缠绕管式反应器在甲醇合成装置上的应用》", 《氮肥技术》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2719441C1 (en) * | 2018-10-22 | 2020-04-17 | Пуцзин Кемикал Индастри Ко., Лтд | Reactor for large-scale synthesis of ethylene glycol |
| CN109734559A (en) * | 2019-03-05 | 2019-05-10 | 西南化工研究设计院有限公司 | The energy saving technique and system of nitrous acid ester regeneration by-product dust technology in ethylene glycol preparation |
| CN109942371A (en) * | 2019-03-20 | 2019-06-28 | 江苏凯美普瑞工程技术有限公司 | Staked type coal-ethylene glycol reaction unit and method |
| WO2021089183A1 (en) * | 2019-11-05 | 2021-05-14 | Linde Gmbh | Process and plant for producing monoethylene glycol |
| CN113912491A (en) * | 2020-07-10 | 2022-01-11 | 中国石油化工股份有限公司 | Method and device for safely preparing dimethyl oxalate in coupling reactor and application of method and device |
| WO2022110871A1 (en) * | 2020-11-30 | 2022-06-02 | 南京延长反应技术研究院有限公司 | Enhanced micro-interface reaction system and method for preparing ethylene glycol by oxalate method |
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