CN106928021A - A kind of method of preparing ethylene glycol by using dimethyl oxalate plus hydrogen - Google Patents
A kind of method of preparing ethylene glycol by using dimethyl oxalate plus hydrogen Download PDFInfo
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- 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
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- 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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- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract
A kind of method of preparing ethylene glycol by using dimethyl oxalate plus hydrogen,Dimethyl oxalate is preheated to gaseous state by preheater,Hybrid concurrency gives birth to hydrogenation reaction during dimethyl oxalate and hydrogen are passed through into the first hydrogenation reactor,Products therefrom is into carrying out gas-liquid separation in the first separator,It is separated into hydrogen and the first liquid product,Hydrogen enters Hydrogen Line and circulates participation hydrogenation reaction,First liquid product is into being separated into methyl alcohol and methyl glycollate in the first destilling tower,Methanol loop returns nitrosation reactor,Methyl glycollate is into carrying out hydrogenation reaction in the second hydrogenation reactor,Products therefrom is separated into hydrogen and second liquid phase product in the second separator,Hydrogen enters pipeline and circulates participation hydrogenation reaction,Second liquid phase product is separated into methyl alcohol and ethylene glycol in after-fractionating tower,Methanol loop is returned in nitrosation reactor and carries out nitrosation reaction,Ethylene glycol is target product.The advantage of the invention is that：Process is simple, feed stock conversion is high, can improve the activity and stability of hydrogenation catalyst.
Description
Technical field
The present invention relates to ethylene glycol preparation field, a kind of especially method of preparing ethylene glycol by using dimethyl oxalate plus hydrogen.
Background technology
Dimethyl oxalate is the important source material of coal-ethylene glycol.Ethylene glycol is a kind of important industrial chemicals, is mainly used as
Polyester dacron processed, polyester resin, can resin PET processed, i.e. polyethylene terephthalate, fibre-grade PET is polyster fibre,
Bottle piece level PET is used to make mineral water bottle etc..Can also alkyd resin processed, glyoxal etc., also serve as antifreezing agent etc., purposes is suitable
Extensively.Nearly ten years, because domestic PET industry demand constantly rises, importation dependence is up to more than 60%, the country all the time
Yield breach is larger.The few oil of China's richness coal, is increasingly taken seriously with coal-ethylene glycol technology, coal-ethylene glycol commercial plant day
Benefit increases.Coal-ethylene glycol route mainly includes two steps, and one is that dimethyl oxalate is obtained by raw material of CO, and two is dimethyl oxalate
It is hydrogenated to ethylene glycol.In recent years, each scientific research institution to the research of Hydrogenation of Dimethyl Oxalate catalyst more gets up.The country, such as
The research aircrafts such as Fujian Inst. of Matter Structure, Chinese Academy of Sciences, East China University of Science, University Of Tianjin, Fudan University, Zhejiang University
Research of the structure in terms of oxalate hydrogenation catalyst is engaged in, particularly nearly 5 years documents are more.
A kind of existing Application No. CN201110095830.3 is entitled《The side of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol
Method》Chinese invention patent disclose a kind of method by hydrogenation of dimethyl oxalate to synthesizing ethylene glycol, with dimethyl oxalate and hydrogen
Gas is raw material, is comprised the following steps：Using the methanol solution of dimethyl oxalate as first burst of liquid phase feed and first gang of hydrogen head
First reactor is introduced into, first burst of product with methyl glycollate as primary product is generated；First burst of product with
Second strand of hydrogen enters second reactor, generates second burst of product with ethylene glycol as primary product.The method can improve
The stability of catalyst.However, the invention does not refer to the preheating of dimethyl oxalate and the separation of hydrogenation products, part is still had
Hydrogen and ethylene glycol contact react, and generate second alcohol and water, and the presence of water can cause hydrogen dividing potential drop unstable, make air pressure in device
Fluctuation, influences production operation, is unfavorable for the stabilization of product property, therefore, it is necessary to further improve the method.
The content of invention
The technical problems to be solved by the invention are directed to above-mentioned state of the art and provide a kind of dimethyl oxalate and add
The method of hydrogen preparing ethylene glycol, with process is simple, feed stock conversion advantage high, and oxalic acid diformazan can be improved using this method
The activity and stability of ester through hydrogenation ethylene glycol catalyst.
The present invention solve the technical scheme that is used of above-mentioned technical problem for：The side of this preparing ethylene glycol by using dimethyl oxalate plus hydrogen
Method, it is characterised in that：Comprise the following steps：
Step one, is preheated to gaseous state, and gaseous dimethyl oxalate and hydrogen are led to using preheater by dimethyl oxalate
Enter mixing in the first hydrogenation reactor；
There is hydrogenation reaction, products therefrom in the first hydrogenation reactor with hydrogen in step 2, gaseous dimethyl oxalate
Gas-liquid separation is carried out into the first separator；
Step 3, the product obtained by step 2 is separated into hydrogen and the first liquid product, the hydrogen in the first separator
Gas enters Hydrogen Line and circulates participation hydrogenation reaction, and first liquid product enters in the first destilling tower；
Step 4, the first liquid product that the first destilling tower will be isolated in the first separator is separated into methyl alcohol and glycolic
Methyl esters, methanol loop is returned in the nitrosation reactor of production dimethyl oxalate and carries out nitrosation reaction, and methyl glycollate enters the
In two hydrogenation reactors；
Step 5, methyl glycollate carries out hydrogenation reaction in the second hydrogenation reactor, and products therefrom enters second and separates
Device carries out gas-liquid separation；
Step 6, step 5 products therefrom is separated into hydrogen and second liquid phase product in the second separator, and hydrogen enters
Pipeline simultaneously circulates participation hydrogenation reaction, and second liquid phase product enters in after-fractionating tower；
Step 7, the second liquid phase product that after-fractionating tower will be isolated in the second separator is separated into methyl alcohol and second two
Alcohol, methanol loop is returned in nitrosation reactor and carries out nitrosation reaction, and ethylene glycol is target product.
Used as improvement, hydrogen and the mol ratio of dimethyl oxalate in the first hydrogenation reactor are 10~20, the second hydrogenation
Hydrogen and the mol ratio of methyl glycollate in reactor are 10~50.
Used as improvement, the preheater temperature is 170~200 DEG C.
Used as improvement, the pressure of first separator is 0.04~0.12MPa, and temperature is 30~50 DEG C.
Used as improvement, second separator pressure is 0.04~0.12MPa, and temperature is 30~50 DEG C.
As improvement, hydrogenation catalyst is filled with described the first hydrogenation reactor, the second hydrogenation reactor, it is described to add
Hydrogen catalyst is by zinc oxide, cupric oxide, tungsten oxide and SiO2Composition, the SiO2It is carrier, the content of the zinc oxide is 20%
~60%, the content of the cupric oxide is 5%~12%, and the tungsten oxide content is 5%~20%, the SiO2Content be
8%~70%, the content is the percentage of oxide mass in a catalyst.
Further improve, the hydrogenation catalyst is reduced with containing the hydrogen nitrogen mixed gas that hydrogen volume is 1%~90%, also
150~400 DEG C of former temperature, reduction is divided into three phases, and the reduction temperature of first stage is 150~250 DEG C, and heating rate 20~
30℃/h；The reduction temperature of second stage is 250~300 DEG C, 15~25 DEG C/h of heating rate；The reduction temperature of phase III is
300~380 DEG C, 10~20 DEG C/h of heating rate, in the first stage, the reduction temperature of second stage and phase III when terminating it is equal
Constant temperature 8 hours.
Further improve, the heating rate of the first stage is 25 DEG C/h, and the heating rate of the second stage is 20
DEG C/h, the heating rate of the phase III is 15 DEG C/h.
Further improve, the temperature of hydrogenation catalyst is reduced to initial temperature by reduction after terminating by cooling device, drop
Warm speed is 15 DEG C/h.
Used as improvement, the pressure of first hydrogenation reactor is 1.2~2.0MPa, and the reaction temperature of hydrogenation reaction is
120~220 DEG C, mass space velocity is 0.1~10.0/h, and the pressure of second hydrogenation reactor is 1.5~2.5MPa, and hydrogenation is anti-
The reaction temperature answered is 150~250 DEG C, and mass space velocity is 0.1~10.0/h.
Compared with prior art, the method for preparing ethylene glycol by using dimethyl oxalate plus hydrogen of the invention has the following advantages that：
1st, dimethyl oxalate enters the first hydrogenation reactor together with hydrogen again after being first preheated to gaseous state, can make oxalic acid two
Methyl esters is more fully contacted with hydrogen, and hydrogenation reaction increases in the possibility that activity of hydrocatalyst centre bit is reacted
Greatly, the conversion ratio of dimethyl oxalate can so be improved；
2nd, hydrogen is separated with liquid product using the first separator and the second separator, can so avoids final purpose
Glycol product is contacted with hydrogen, and react generation second alcohol and water, be it also avoid dimethyl oxalate chance water and is hydrolyzed into oxalic acid, is entered
And the problem of etching apparatus, simultaneous separation of hydrogen gas can ensure the stabilization of hydrogen dividing potential drop in reaction system, help to maintain product property
Stabilization, be also convenient for production operation；
3rd, the hydrogenation catalyst that the inventive method is used instead of price copper conduct relatively high using more cheap zinc
Active component, on the one hand solves the problems, such as copper content copper catalyst high temperature easy-sintering inactivation high, on the other hand significantly reduces
The preparation cost of hydrogenation catalyst；
4th, hydrogenation catalyst is using unique segmentation restoring method, just the divalent zinc of oxidation state be progressively converted into monovalence zinc and
Simple substance zinc, improves the activity of hydrogenation catalyst, makes this hydrogenation catalyst not high using only initial activity, and after long-term operation
Can keep activity stabilized, can effectively extend the cycle of operation of ethylene glycol commercial plant；
5th, after gained methyl alcohol is separated through corresponding destilling tower respectively in the inventive method, profit again is looped back in nitrosation reactor
With so can effectively reducing the cost of material of coal-ethylene glycol.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the embodiment of the present invention.
Specific embodiment
The present invention is described in further detail below in conjunction with accompanying drawing embodiment.
As shown in figure 1, the method for the preparing ethylene glycol by using dimethyl oxalate plus hydrogen of the present embodiment, comprises the following steps：Step one,
Dimethyl oxalate 1 is preheated to gaseous state using preheater 3, gaseous dimethyl oxalate 1 and hydrogen 2 are passed through the first hydrogenation reaction
Mix in device 4；There is hydrogenation reaction, gained in the first hydrogenation reactor 4 with hydrogen 2 in step 2, gaseous dimethyl oxalate 1
Product is into carrying out gas-liquid separation in the first separator 5；Step 3, the product obtained by step 2 is separated in the first separator 5
It is the liquid product 7 of hydrogen 2 and first, the hydrogen 2 is into pipeline 6 and circulates participation hydrogenation reaction, first liquid product 7
Into in the first destilling tower 8；Step 4, the first liquid product 7 that the first destilling tower 8 will be isolated in first separator 5 is separated
It is methyl alcohol 9 and methyl glycollate 10, methyl alcohol 9 to loop back that carry out nitrosation in the nitrosation reactor of production dimethyl oxalate anti-
Should, methyl glycollate 10 enters in the second hydrogenation reactor 11；Step 5, methyl glycollate enters in the second hydrogenation reactor 11
Row hydrogenation reaction, products therefrom carries out gas-liquid separation into the second separator 12；Step 6, step 5 products therefrom is at second point
Hydrogen 2 and second liquid phase product 14 are separated into device 12, hydrogen 2 is into pipeline 6 and circulates participation hydrogenation reaction, second liquid phase
Product 14 enters in after-fractionating tower 15；Step 7, the second liquid phase that after-fractionating tower 15 will be isolated in second separator 12
Product 14 is separated into methyl alcohol 9 and ethylene glycol 13, and methyl alcohol 9 carries out nitrosation reaction, ethylene glycol 13 in looping back nitrosation reactor
It is target product.
Hydrogen 2 and the mol ratio of dimethyl oxalate 1 in first hydrogenation reactor 4 are 10~20, the second hydrogenation reactor
Hydrogen 2 and the mol ratio of methyl glycollate 10 in 11 are 10~50.The temperature of the preheater 3 is 170~200 DEG C.It is described
The pressure of the first separator 5 is 0.04~0.12MPa, and temperature is 30~50 DEG C.The pressure of second separator 12 is 0.04
~0.12MPa, temperature is 30~50 DEG C.Hydrogenation catalyst is filled with first hydrogenation reactor 4, the second hydrogenation reactor 11,
The hydrogenation catalyst is by zinc oxide, cupric oxide, tungsten oxide and SiO2Composition, the SiO2It is carrier, the content of the zinc oxide
It is 20%~60%, the content of the cupric oxide is 5%~12%, and the tungsten oxide content is 5%~20%, the SiO2's
Content is 8%~70%, and the content is the percentage of oxide mass in a catalyst.Hydrogenation catalyst is with containing hydrogen volume
Hydrogen nitrogen mixed gas for 1%~90% are reduced, 150~400 DEG C of reduction temperature, and reduction is divided into three phases, first stage
Reduction temperature be 150~250 DEG C, 20~30 DEG C/h of heating rate；The reduction temperature of second stage is 250~300 DEG C, is heated up
15~25 DEG C/h of speed；The reduction temperature of phase III is 300~380 DEG C, 10~20 DEG C/h of heating rate, in the first stage,
The equal constant temperature of reduction temperature when second stage and phase III terminate 8 hours.The heating rate of first stage is 25 DEG C/h, described
The heating rate of second stage is 20 DEG C/h, and the heating rate of the phase III is 15 DEG C/h.Reduction passes through cooling after terminating
The temperature of hydrogenation catalyst is reduced to initial temperature by device, and rate of temperature fall is 15 DEG C/h.The pressure of the first hydrogenation reactor 4 is
1.2~2.0MPa, the reaction temperature of hydrogenation reaction is 120~220 DEG C, and mass space velocity is 0.1~10.0/h, second hydrogenation
The pressure of reactor 11 is 1.5~2.5MPa, and the reaction temperature of hydrogenation reaction is 150~250 DEG C, mass space velocity is 0.1~
10.0/h。
The preheated device 3 of the elder generation of dimethyl oxalate 1 is preheated to gaseous state, then mixes with the first hydrogenation reactor 4 of entrance of hydrogen 2,
After hydrogenated reaction, products therefrom separates the liquid product 7 of hydrogen 2 and first of surplus through the first separator 5, and hydrogen 2 is looped back
The circulation of pipeline 6 participates in hydrogenation reaction, and the first liquid product 7 is into being separated into methyl alcohol 9 and ethanol ester methyl ester in the first destilling tower 8
10, methyl alcohol 9 is used to manufacture methyl nitrite in looping back nitrosation reactor, and ethanol ester methyl ester 10 enters the second hydrogenation reactor
11, after hydrogenated reaction, products therefrom carries out gas-liquid separation into the second separator 12, obtains the complete hydrogen 2 of unreacted and
Two liquid products 14, hydrogen 2 loops back the circulation of pipeline 6 and participates in hydrogenation reaction, and second liquid phase product 14 enters destilling tower 15, through steaming
Evaporate and obtain methyl alcohol 9 and purpose product ethylene glycol 13, methyl alcohol 9 is used to manufacture methyl nitrite, second in looping back nitrosation reactor
The ejector of glycol 13 is collected standby.
Specifically, preheater is heated to 170~200 DEG C and dimethyl oxalate is heated to be into gaseous state, then by gaseous oxalic acid
Dimethyl ester is passed through in the first hydrogenation reactor with hydrogen and mixes, and hydrogenation of the present invention is filled with the first hydrogenation reactor and is urged
Agent.Pressure in first hydrogenation reactor is 1.2~2.0MPa, and reaction temperature is 120~220 DEG C, mass space velocity is 0.1~
10.0/h.After hydrogenated reaction, products therefrom separates the hydrogen and the first liquid product of surplus through the first separator, and first separates
Device pressure is 0.04~0.12MPa, and temperature is 30~50 DEG C, and the exess of H2 gas return pipe road is recycled, and the first liquid product enters
The isolated methyl alcohol of first destilling tower and methyl glycollate, methanol loop returns nitrosation reactor to be used to manufacture methyl nitrite.
Mol ratio into the hydrogen in the first hydrogenation reactor and dimethyl oxalate is 10~20.Methyl glycollate is in the first step
Reaction yield is 90%~100%.Methyl glycollate enters the second hydrogenation reactor, is filled with above in the second hydrogenation reactor
The hydrogenation catalyst mentioned, the operating pressure of the second hydrogenation reactor is 1.5~2.5MPa, and reaction temperature is 150~250 DEG C,
Mass space velocity is 0.1~10.0/h.After hydrogenated reaction, all products carry out gas-liquid separation, second point into the second separator
It is 0.04~0.12MPa from device pressure, temperature is 30~50 DEG C, obtains the hydrogen and second liquid phase product of surplus, and hydrogen is still returned
Circulated to pipeline, the second hydrogenation reactor gained second liquid phase product enters after-fractionating tower, and methyl alcohol and purpose are obtained through distillation
Product ethylene glycol, methanol loop returns nitrosation reactor to be used to manufacture methyl nitrite.Hydrogen and ethanol in second reactor
The mol ratio of sour methyl esters is 10~50.During this because in time separating hydrogen with product, it is to avoid ethylene glycol reacts with hydrogen
Generation water.
In the inventive method, described hydrogenation catalyst is by zinc oxide, cupric oxide, tungsten oxide and SiO2Composition, the SiO2
It is carrier, the content of the zinc oxide is 20%~60%, and the content of the cupric oxide is 5%~12%, and the tungsten oxide contains
It is 5%~20% to measure, the SiO2Content be 8%~70%, the content is hundred of oxide mass in a catalyst
Divide ratio.The hydrogenation catalyst is reduced with containing the hydrogen nitrogen mixed gas that hydrogen volume is 1%~90%, reduction temperature 150~400
DEG C, reduction is divided into three phases, and the reduction temperature of first stage is 150~250 DEG C, 20~30 DEG C/h of heating rate；Second-order
The reduction temperature of section is 250~300 DEG C, 15~25 DEG C/h of heating rate；The reduction temperature of phase III is 300~380 DEG C, is risen
10~20 DEG C/h of warm speed, in the first stage, the equal constant temperature of reduction temperature of second stage and phase III when terminating 8 hours.Also
The temperature of hydrogenation catalyst is reduced to initial temperature by original after terminating by cooling device, and rate of temperature fall is 15 DEG C/h.
The present invention is described further by embodiment below, but is not limited only to the present embodiment.
The preparation of hydrogenation catalyst A：
By 22gZn (NO3)2·6H2O and 22gNH4HCO3It is each configured to 500ml solution；The silicon of 50g concentration 30% is molten
Glue is added in a container with stirring parallel with above-mentioned zinc solution, precipitant solution；It is warming up to 100 DEG C and evaporates most of water
Point, and make Precipitation, and the precipitation is washed three times, finally dry；ZnSi catalyst precursors prepared by above-mentioned co-precipitation
The solution that 4g copper nitrates and 8g nitric acid tungsten are prepared is impregnated again；The catalyst precursor of this impregnation aids is calcined 8h at 350 DEG C,
Most it is molded through forming machine afterwards, obtains final product catalyst A.
Catalyst A is respectively charged into in the first hydrogenation reactor and hydrogenation second reactor, in two reactors are
The tubular reactor of footpath 20mm.Using preceding using 10%H2-N2Gas is reduced, 150~400 DEG C of reduction temperature.Reduction is divided into three ranks
Section, 150~250 DEG C of initial stage, 25 DEG C/h of heating rate, after temperature rises to 250 DEG C, constant temperature 8 hours；250~300 DEG C of mid-term,
20 DEG C/h of heating rate, constant temperature 8 hours when temperature is raised to 300 DEG C；300~380 DEG C of latter stage, 15 DEG C/h of heating rate works as temperature
Constant temperature 8 hours when degree rises to 380 DEG C.Segmentation reduction obtains activity hydrogenation catalyst higher after terminating.In order to anti-needed for reaching
Temperature is answered, can be lowered the temperature with 10 DEG C/h of rate of temperature fall.
Embodiment 1
Preheater is heated to 160 DEG C and dimethyl oxalate is heated to be into gaseous state, then is mixed into the first hydrogenation reaction with hydrogen
Device, the operating pressure of the first hydrogenation reactor is 1.5MPa, and reaction temperature is 200 DEG C, and hydrogen ester ratio is 100: 1, and mass space velocity is
0.6/h.After hydrogenated reaction, products therefrom separates the hydrogen and the first liquid product of surplus through the first separator, and first separates
Device pressure is 0.08MPa, and temperature is 40 DEG C, and the exess of H2 gas return pipe road is recycled, and the first liquid product enters the first destilling tower
Isolated methyl alcohol and methyl glycollate, methanol loop returns nitrosation reactor to be used to manufacture methyl nitrite.Add into first
Dimethyl oxalate and the mol ratio of hydrogen in hydrogen reactor are 1: 20.
Methyl glycollate enters in the second hydrogenation reactor, and the operating pressure of the second hydrogenation reactor is 2.0MPa, reaction
Temperature is 210 DEG C, and hydrogen ester ratio is 100: 1, and mass space velocity is 0.5/h.After hydrogenated reaction, all products enter the second separator
Gas-liquid separation is carried out, the second separator pressure is 0.09MPa, and temperature is 45 DEG C, obtains the hydrogen and second liquid phase product of surplus,
The exess of H2 gas return pipe road is recycled, and the second hydrogenation reactor gained second liquid phase product enters after-fractionating tower, through distilling
To methyl alcohol and purpose product ethylene glycol, methanol loop returns nitrosation reactor to be used to manufacture methyl nitrite.Into the second reaction
Methyl glycollate and the mol ratio of hydrogen in device are 1: 40.
Final reaction result is：The conversion ratio 99.7% of dimethyl oxalate, the selectivity of ethylene glycol is 97.4%.First
After hydrogenation catalyst is operated through 3000h in hydrogenation reactor and the second hydrogenation reactor, substantially inactivation is not found.
Embodiment 2
Preheater is heated to 200 DEG C and dimethyl oxalate is heated to be into gaseous state, then is mixed into the first hydrogenation reaction with hydrogen
Device, the operating pressure of the first hydrogenation reactor is 1.2MPa, and reaction temperature is 180 DEG C, and hydrogen ester ratio is 80: 1, and mass space velocity is
0.5/h.After hydrogenated reaction, products therefrom separates the hydrogen and the first liquid product of surplus through the first separator, and first separates
Device pressure is 0.09MPa, and temperature is 45 DEG C, and the exess of H2 gas return pipe road is recycled, and the first liquid product enters the first destilling tower
Isolated methyl alcohol and methyl glycollate, methanol loop returns nitrosation reactor to be used to manufacture methyl nitrite.Add into first
Dimethyl oxalate and the mol ratio of hydrogen in hydrogen reactor are 1: 15.
Methyl glycollate enters in the second hydrogenation reactor, and the operating pressure of the second hydrogenation reactor is 2.2MPa, reaction
Temperature is 190 DEG C, and hydrogen ester ratio is 80: 1, and mass space velocity is 0.7/h.After hydrogenated reaction, all products enter the second separator
Gas-liquid separation is carried out, the second separator pressure is 0.1MPa, and temperature is 50 DEG C, obtains the hydrogen and second liquid phase product of surplus,
The exess of H2 gas return pipe road is recycled, and the second hydrogenation reactor gained second liquid phase product enters after-fractionating tower, through distilling
To methyl alcohol and purpose product ethylene glycol, methanol loop returns nitrosation reactor to be used to manufacture methyl nitrite.Into the second reaction
Methyl glycollate and the mol ratio of hydrogen in device are 1: 30.
Final reaction result is：The conversion ratio 99.6% of dimethyl oxalate, the selectivity of ethylene glycol is 96.5%.First
After hydrogenation catalyst is operated through 3000h in hydrogenation reactor and the second hydrogenation reactor, substantially inactivation is not found.
Embodiment 3
Preheater is heated to 180 DEG C and dimethyl oxalate is heated to be into gaseous state, then is mixed into the first hydrogenation reaction with hydrogen
Device, the operating pressure of the first hydrogenation reactor is 1.4MPa, and reaction temperature is 150 DEG C, and hydrogen ester ratio is 120: 1, and mass space velocity is
1.0/h.After hydrogenated reaction, products therefrom separates the hydrogen and the first liquid product of surplus through the first separator, and first separates
Device pressure is 0.1MPa, and temperature is 50 DEG C, and the exess of H2 gas return pipe road is recycled, and the first liquid product divides into the first destilling tower
From methyl alcohol and methyl glycollate is obtained, methanol loop returns nitrosation reactor to be used to manufacture methyl nitrite.Into the first hydrogenation
Dimethyl oxalate and the mol ratio of hydrogen in reactor are 1: 10.
Methyl glycollate enters in the second hydrogenation reactor, and the operating pressure of the second hydrogenation reactor is 1.7MPa, reaction
Temperature is 230 DEG C, and hydrogen ester ratio is 120: 1, and mass space velocity is 0.4/h.After hydrogenated reaction, all products enter the second separator
Gas-liquid separation is carried out, the second separator pressure is 0.07MPa, and temperature is 30 DEG C, obtains the hydrogen and second liquid phase product of surplus,
The exess of H2 gas return pipe road is recycled, and the second hydrogenation reactor gained second liquid phase product enters after-fractionating tower, through distilling
To methyl alcohol and purpose product ethylene glycol, methanol loop returns nitrosation reactor to be used to manufacture methyl nitrite.Into the second reaction
Methyl glycollate and the mol ratio of hydrogen in device are 1: 50.
Final reaction result is：The conversion ratio 99.4% of dimethyl oxalate, the selectivity of ethylene glycol is 96.8%.First
After hydrogenation catalyst is operated through 3000h in hydrogenation reactor and the second hydrogenation reactor, substantially inactivation is not found.
Although the present invention is described in detail by above example, it is not limited to this.Above-described embodiment is only
The purpose for enumerating, it can have various modifications, skilled artisans appreciate that these deformations fall within the scope of the present invention.
Claims (10)
1. a kind of method of preparing ethylene glycol by using dimethyl oxalate plus hydrogen, it is characterised in that：Comprise the following steps：
Step one, gaseous state is preheated to using preheater (3) by dimethyl oxalate (1), by gaseous dimethyl oxalate (1) and hydrogen
(2) it is passed through mixing in the first hydrogenation reactor (4)；
There is hydrogenation reaction, gained in the first hydrogenation reactor (4) with hydrogen (2) in step 2, gaseous dimethyl oxalate (1)
Product enters in the first separator (5) carries out gas-liquid separation；
Step 3, the product obtained by step 2 is separated into hydrogen (2) and the first liquid product (7), institute in the first separator (5)
State hydrogen (2) to enter pipeline (6) and circulate participation hydrogenation reaction, first liquid product (7) enters the first destilling tower (8)
In；
Step 4, the first liquid product (7) that the first destilling tower (8) will be isolated in the first separator (5) is separated into methyl alcohol (9)
With methyl glycollate (10), methyl alcohol (9) loop back production dimethyl oxalate nitrosation reactor in carry out nitrosation reaction, second
Alkyd methyl esters (10) enters in the second hydrogenation reactor (11)；
Step 5, methyl glycollate carries out hydrogenation reaction in the second hydrogenation reactor (11), and products therefrom enters second and separates
Device (12) carries out gas-liquid separation；
Step 6, step 5 products therefrom is separated into hydrogen (2) and second liquid phase product (14), hydrogen in the second separator (12)
Gas (2) enters pipeline (6) and circulates participation hydrogenation reaction, and second liquid phase product (14) enters in after-fractionating tower (15)；
Step 7, the second liquid phase product (14) that after-fractionating tower (15) will be isolated in the second separator (12) is separated into methyl alcohol
(9) and ethylene glycol (13), methyl alcohol (9) carries out nitrosation reaction in looping back nitrosation reactor, and ethylene glycol (13) is that target is produced
Thing.
2. method according to claim 1, it is characterised in that：Hydrogen (2) and oxalic acid two in first hydrogenation reactor (4)
The mol ratio of methyl esters (1) is 10~20, hydrogen (2) in the second hydrogenation reactor (11) and methyl glycollate (10) mole
Than being 10~50.
3. method according to claim 1, it is characterised in that：The temperature of the preheater (3) is 170~200 DEG C.
4. method according to claim 1, it is characterised in that：The pressure of first separator (5) be 0.04~
0.12MPa, temperature is 30~50 DEG C.
5. method according to claim 1, it is characterised in that：The pressure of second separator (12) be 0.04~
0.12MPa, temperature is 30~50 DEG C.
6. method according to claim 1, it is characterised in that：Described the first hydrogenation reactor (4), the second hydrogenation reaction
Hydrogenation catalyst is filled with device (11), the hydrogenation catalyst is by zinc oxide, cupric oxide, tungsten oxide and SiO2Composition, it is described
SiO2It is carrier, the content of the zinc oxide is 20%~60%, the content of the cupric oxide is 5%~12%, the oxidation
W content is 5%~20%, the SiO2Content be 8%~70%, the content is oxide mass in a catalyst
Percentage.
7. method according to claim 6, it is characterised in that：The hydrogenation catalyst is 1%~90% with containing hydrogen volume
Hydrogen nitrogen mixed gas reduced, 150~400 DEG C of reduction temperature, reduction be divided into three phases, the reduction temperature of first stage is
150~250 DEG C, 20~30 DEG C/h of heating rate；The reduction temperature of second stage is 250~300 DEG C, heating rate 15~25
℃/h；The reduction temperature of phase III be 300~380 DEG C, 10~20 DEG C/h of heating rate, in the first stage, second stage and
The equal constant temperature of reduction temperature when phase III terminates 8 hours.
8. method according to claim 7, it is characterised in that：The heating rate of the first stage is 25 DEG C/h, described
The heating rate of second stage is 20 DEG C/h, and the heating rate of the phase III is 15 DEG C/h.
9. method according to claim 7, it is characterised in that：Reduction passes through cooling device by hydrogenation catalyst after terminating
Temperature is reduced to initial temperature, and rate of temperature fall is 15 DEG C/h.
10. method according to claim 1, it is characterised in that：The pressure of first hydrogenation reactor (4) be 1.2~
2.0MPa, the reaction temperature of hydrogenation reaction is 120~220 DEG C, and mass space velocity is 0.1~10.0/h, second hydrogenation reaction
The pressure of device (11) is 1.5~2.5MPa, and the reaction temperature of hydrogenation reaction is 150~250 DEG C, and mass space velocity is 0.1~10.0/
h。
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Cited By (6)
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| CN109987582A (en) * | 2019-04-15 | 2019-07-09 | 余菲 | A kind of full liquid phase hydrogenation technology |
| CN110483241A (en) * | 2019-08-19 | 2019-11-22 | 易高环保能源研究院有限公司 | The method and apparatus of preparation of ethanediol by dimethyl oxalate hydrogenation |
| CN112479822A (en) * | 2020-11-30 | 2021-03-12 | 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 |
| CN112479814A (en) * | 2019-09-12 | 2021-03-12 | 南京延长反应技术研究院有限公司 | Reaction system and process for strengthening hydrogenation of dimethyl oxalate in coal-to-ethylene glycol |
| CN112759505A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method and system for preparing ethylene glycol |
| CN116041146A (en) * | 2022-12-19 | 2023-05-02 | 常州大学 | Glycol hydrofining method and equipment |
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| CN102649686A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for synthesizing ethylene glycol |
| CN102649706A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol through gas phase hydrogenation of oxalate |
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| CN109987582A (en) * | 2019-04-15 | 2019-07-09 | 余菲 | A kind of full liquid phase hydrogenation technology |
| CN109987582B (en) * | 2019-04-15 | 2020-01-07 | 余菲 | Full liquid phase hydrogenation technology |
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| CN112479814A (en) * | 2019-09-12 | 2021-03-12 | 南京延长反应技术研究院有限公司 | Reaction system and process for strengthening hydrogenation of dimethyl oxalate in coal-to-ethylene glycol |
| CN112759505A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method and system for preparing ethylene glycol |
| CN112759505B (en) * | 2019-10-21 | 2024-01-30 | 中国石油化工股份有限公司 | Method and system for preparing ethylene glycol |
| CN112479822A (en) * | 2020-11-30 | 2021-03-12 | 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 |
| CN116041146A (en) * | 2022-12-19 | 2023-05-02 | 常州大学 | Glycol hydrofining method and equipment |
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