CN206599529U - A kind of device of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol - Google Patents
A kind of device of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol Download PDFInfo
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- CN206599529U CN206599529U CN201720206605.5U CN201720206605U CN206599529U CN 206599529 U CN206599529 U CN 206599529U CN 201720206605 U CN201720206605 U CN 201720206605U CN 206599529 U CN206599529 U CN 206599529U
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- hydrogenation reactor
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- hydrogenation
- ethylene glycol
- dimethyl oxalate
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Abstract
A kind of device of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol, including the first hydrogenation reactor and the second hydrogenation reactor being arranged in parallel, air pressure balancer, 3rd hydrogenation reactor, first hydrogenation reactor is connected with that can be passed through the pipeline of dimethyl oxalate and hydrogen mixed gas respectively with the air inlet of the second hydrogenation reactor, the reversal valve that gaseous mixture is passed through the first hydrogenation reactor or the second hydrogenation reactor by selection is provided with pipeline, the outlet of first hydrogenation reactor and the second hydrogenation reactor is connected with the import of the 3rd hydrogenation reactor, the outlet of 3rd hydrogenation reactor is connected with ethylene glycol collection portion, first hydrogenation reactor, second hydrogenation reactor, 3rd hydrogenation reactor is connected with air pressure balancer respectively.It the advantage is that:Pre-hydrogenator pattern is introduced, the catalyzer temperature-elevating of reactor top filling is not obvious, is less prone to coking phenomenon, the activity of catalyst can be kept for a long time, so as to reduce the replacement frequency of catalyst, improves the efficiency of production ethylene glycol.
Description
Technical field
The utility model is related to ethylene glycol preparing technical field, especially a kind of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol
Device.
Background technology
Ethylene glycol (Ethylene Glycol, abbreviation EG) also known as glycol, are most simple and most important binary aliphatics
Alcohol, is also a kind of important Organic Chemicals, available for producing a variety of chemical products, such as polyester fiber, antifreezing agent, unsaturation
Polyester resin, lubricant, plasticizer, nonionic surfactant, explosive, coating and ink etc., application field is widely.Second
Glycol is heated under catalyst (manganese dioxide, aluminum oxide, zinc oxide or sulfuric acid) effect, can occur intramolecular or intermolecular mistake
Water.Ethylene glycol can act on forming alkoxide with alkali metal or alkaline-earth metal.In process hides and pharmaceuticals industry, be used separately as hydrating agents and
Solvent.The traditional industry production method of ethylene glycol is that epoxyethane water is legal.Route technological process length, high energy consumption, the ethylene glycol
Selectivity is low, and this method belongs to petrochemical industry route, big to petroleum resources dependence, and ethylene glycol price fluctuates width with crude oil price
Degree is big.Therefore, ethylene glycol is prepared by the Non oil-based route based on natural gas or coal-based feedstocks for the China of the few oil of many coals to have
There is extremely important meaning.
Synthesis gas indirect method synthesizing glycol, i.e., from carbon monoxide, coupling obtains oxalate diester, then through oxalic acid two
Ester catalysis is hydrogenated with the route of carbon one of preparing ethylene glycol, is to be acknowledged as a kind of technical and better economy process route recently.
1966, American Association oil company disclosed CO, alcohol and oxygen with PdCl2-CuCl2For the condition of catalyst
Under, the patent of synthesis of oxalic acid dialkyl ester is reacted under 125 DEG C, 7.0MPa.Reaction equation is as follows:
2ROH+2CO+1/2O2→(COOR)2+H2O
This method is due to using chloride catalyst, and equipment corrosion is serious.Further, since water is the persistent erection poisonous substance of catalyst
Matter, to keep reaction system anhydrous state, it is necessary to using a large amount of dehydrating agents, cause the course of reaction less economical, is difficult to realize
Industrialization.Hereafter, U.S. ARCO companies and company of Ube Industries Ltd. are improved catalyst system, but still fail to solve
Equipment corrosion problem.Afterwards, Yu Buxingchan companies and UCC companies of the U.S. have developed jointly the new technology road of synthesis of oxalic acid diester
Line, the technique uses 2% palladium catalyst using activated carbon as carrier, is 90 DEG C, under 9.8MPa in reaction condition, introduces nitrous
Acid esters, makes CO be coupled with butanol, the problems such as solving the corrosion of former method, and builds up a set of 6000 tons/year of oxalic acid two fourth
The commercial plant of ester, but this method oxalate generating rate is slow, and accessory substance is more, and hydrogenation will be carried out in more than 20MPa.1977
Ube Industries Ltd. proposes normal pressure gas-phase synthesis of oxalate technology, and the technology is with Pd/Al2O3For catalyst, in temperature 80~150
DEG C, under the conditions of pressure 0.5MPa, CO and methyl nitrite or butyl nitrite carry out gas phase reaction generation oxalate, and its yield reaches
To 98%.After oxalate diester is purified, gas phase hydrogenation reaction generation second two is carried out under the conditions of Cu-Cr catalyst, 3MPa, 225 DEG C
Alcohol, glycol selectivity is 95%.In the early 1980s, the country, which has also begun to CO, catalyzes and synthesizes oxalate and its derivative produce
The research of product oxalic acid, ethylene glycol.Fujian thing structure institute of the Chinese Academy of Sciences and Nan Jing's synthesis ammonia plant cooperation, are reclaimed using synthetic ammonia installation
CO, the catalytic coupling synthesizing dimethyl oxalate at normal pressure, 150 DEG C, then using Cu/Cr as catalyst, carry out dimethyl oxalate
Low-voltage hydrogenation, conversion ratio is up to 95%~100%, and glycol selectivity is 80%~90%." National Development and Reform Commission is on rule
The notice of model Chemical Industry orderly development "《Send out industry [2011] 635 of changing products》Middle regulation, to strengthen to Developing Coal Chemical Industry
Macro adjustments and controls and guiding, it is less than 200,000 tons/year of coal-ethylene glycol device to forbid construction scale.《Industry restructuring refers to
Lead catalogue (sheet in 2011) (2013 amendment)》The first kind encourages the 4th article of class Section 11:200000 tons/year and above synthesis gas system
Ethylene glycol.Therefore, synthesizing glycol is large-scale turns to trend of the times.
A kind of existing Patent No. CN201611070201.4 is entitled《A kind of calcium carbide coproduction glycol unit and method》
Chinese invention patent disclose a kind of calcium carbide coproduction glycol unit and method, be related to calcium carbide production technology circulation of tail gas utilization
Technical field, the problem of producing the tail gas pollution environment produced during calcium carbide for solution.The calcium carbide coproduction glycol unit
In, offgas outlet and the pressure-variable adsorption of heat accumulating type calcium carbide production unit extract carbon monoxide unit and are connected;Pressure-variable adsorption extracts hydrogen
The hydrogen outlet of gas unit is connected with ethylene glycol production unit, and pressure-variable adsorption extracts the offgas outlet and pressure-variable adsorption of hydrogen unit
Extract the connection of carbon monoxide unit;Pressure-variable adsorption extracts resolution gas outlet and the heat accumulating type calcium carbide production unit of carbon monoxide unit
Connection, the carbon monoxide outlet that pressure-variable adsorption extracts carbon monoxide unit is connected with ethylene glycol production unit.The calcium carbide coproduction
In glycol unit, hydrogen and carbon monoxide are extracted in the tail gas that will be produced when producing calcium carbide to be used to produce ethylene glycol, is improved
The waste gas utilization rate produced during production calcium carbide, reduces exhaust emissions amount.However, because dimethyl oxalate and hydrogen are in dress
Put middle reaction violent, the catalyst in the device easily produces coking phenomenon, bonding on the reaction vessel, influences catalytic effect,
Cleaning replacement is also inconvenient, therefore the structure of the device also needs further improvement.
The content of the invention
Technical problem to be solved in the utility model is to provide a kind of oxalic acid diformazan for above-mentioned state of the art
The device of ester through hydrogenation synthesizing glycol, with occupying little space, catalyst is difficult coking, advantage easy to clean during reaction.
The utility model solve the technical scheme that is used of above-mentioned technical problem for:This dimethyl oxalate hydrogenation synthesis second two
The device of alcohol, it is characterised in that:Including the first hydrogenation reactor and the second hydrogenation reactor being arranged in parallel, air pressure balancer,
3rd hydrogenation reactor, the air inlet of first hydrogenation reactor and the second hydrogenation reactor is respectively with that can be passed through oxalic acid diformazan
Ester is connected with the pipeline of hydrogen mixed gas, selection is provided with the pipeline gaseous mixture is passed through into the first hydrogenation reactor or the
The reversal valve of two hydrogenation reactors, outlet and the 3rd hydrogenation reactor of first hydrogenation reactor and the second hydrogenation reactor
Import be connected, the outlet of the 3rd hydrogenation reactor is connected with ethylene glycol collection portion, first hydrogenation reactor,
Second hydrogenation reactor, the 3rd hydrogenation reactor is connected with air pressure balancer respectively.
As an improvement, first hydrogenation reactor, the second hydrogenation reactor are shell and tube reactor or plate-type reactor
Again or it is provided with the compound reactor of tubulation and dividing plate.
Further improve, when the first hydrogenation reactor, the second hydrogenation reactor are shell and tube reactor or compound reaction
During device, the tubulation length in first hydrogenation reactor, the second hydrogenation reactor is 1~3m.
As an improvement, the 3rd hydrogenation reactor is the compound reactor for being provided with tubulation and dividing plate.
Further improve, the volume of the 3rd hydrogenation reactor is more than the first hydrogenation reactor or the second hydrogenation reactor
Volume.
As an improvement, being provided with pressure on first hydrogenation reactor, the second hydrogenation reactor, the 3rd hydrogenation reactor
Force snesor, temperature sensor and can be passed through first hydrogenation reactor, the second hydrogenation reactor, the 3rd hydrogenation reactor
Flow detector is provided with the pipeline of dimethyl oxalate and hydrogen mixed gas.
Compared with prior art, the present invention is using the first hydrogenation reactor and the second hydrogenation reaction for including being arranged in parallel
Device, air pressure balancer, the 3rd hydrogenation reactor, the air inlet of first hydrogenation reactor and the second hydrogenation reactor respectively with
Dimethyl oxalate can be passed through with the pipeline of hydrogen mixed gas to be connected, selection is provided with the pipeline gaseous mixture is passed through first
The reversal valve of hydrogenation reactor or the second hydrogenation reactor, the outlet of first hydrogenation reactor and the second hydrogenation reactor with
The import of 3rd hydrogenation reactor is connected, and the outlet of the 3rd hydrogenation reactor is connected with ethylene glycol collection portion, described
First hydrogenation reactor, the second hydrogenation reactor, the 3rd hydrogenation reactor is connected with air pressure balancer respectively.This structure
Advantage is:The gaseous mixture of introducing pre-hydrogenator pattern, dimethyl oxalate and hydrogen is in the first hydrogenation reactor and second
Switching is not stopped between hydrogenation reactor, the catalyzer temperature-elevating of reactor top filling is not obvious, is less prone to coking phenomenon, can grow
Time keeps the activity of catalyst, so as to reduce the replacement frequency of catalyst, improves the efficiency of production ethylene glycol, device cleaning
It is more convenient;Acutely, air pressure change is fast, and air pressure balancer can adjust the pressure of hydrogenation reactor for hydrogenation reaction heat release, it is to avoid plus
Hydrogen reactor internal pressure is excessive to cause danger, while steam recycling can be collected, reduces production cost and energy consumption, improves
Economic benefit.
Brief description of the drawings
Fig. 1 is the structural representation of the utility model embodiment.
Embodiment
The utility model is described in further detail below in conjunction with accompanying drawing embodiment.
As shown in figure 1, the device of the present embodiment hydrogenation of dimethyl oxalate to synthesizing ethylene glycol, including first be arranged in parallel add
The hydrogenation reactor 2 of hydrogen reactor 1 and second, air pressure balancer 4, the 3rd hydrogenation reactor 3, first hydrogenation reactor 1 with
The air inlet of second hydrogenation reactor 2 is connected with that can be passed through the pipeline 5 of dimethyl oxalate and hydrogen mixed gas respectively, the pipe
The reversal valve that gaseous mixture is passed through the first hydrogenation reactor 1 or the second hydrogenation reactor 2 by selection, described first are provided with road 5
The outlet of the hydrogenation reactor 2 of hydrogenation reactor 1 and second is connected with the import of the 3rd hydrogenation reactor 3, the 3rd hydrogenation
The outlet of reactor 3 is connected with ethylene glycol collection portion, first hydrogenation reactor 1, the second hydrogenation reactor 2, and the 3rd adds
Hydrogen reactor 3 is connected with air pressure balancer 4 respectively.First hydrogenation reactor 1, the second hydrogenation reactor 2 are shell and tube
Reactor or plate-type reactor again or are provided with the compound reactor of tubulation and dividing plate.When the first hydrogenation reactor 1, second adds
When hydrogen reactor 2 is shell and tube reactor or compound reactor, in first hydrogenation reactor 1, the second hydrogenation reactor 2
Tubulation length be 1~3m.3rd hydrogenation reactor 3 is the compound reactor for being provided with tubulation and dividing plate.Described
The volume of three hydrogenation reactors 3 is more than the volume of the first hydrogenation reactor 1 or the second hydrogenation reactor 2.First hydrogenation is anti-
Answer device 1, the second hydrogenation reactor 2, be provided with pressure sensor on the 3rd hydrogenation reactor 3, temperature sensor, described first
Hydrogenation reactor 1, the second hydrogenation reactor 2, the 3rd hydrogenation reactor 3 and can be passed through leather dimethyl phthalate and hydrogen mixed gas pipe
Flow detector is provided with road.First hydrogenation reactor 1 and the second hydrogenation reactor 2 share an air pressure balancer 4.
The application method of the device of this hydrogenation of dimethyl oxalate to synthesizing ethylene glycol, comprises the following steps:It is passed through into pipeline
The ratio of hydrogen and dimethyl oxalate is 20~150 in dimethyl oxalate and hydrogen formation gaseous mixture, the gaseous mixture;Control is changed
Gaseous mixture is passed through in the first hydrogenation reactor 1 or the second hydrogenation reactor 2 to valve selection, hydrogenation reaction, reaction pressure is carried out
1.5~4.0MPaG, 145~285 DEG C of reaction temperature, catalyst system is Cu/SiO2, react for gas phase fast reaction, during reaction
Between 1~10s;Above-mentioned reacted product, which enters, carries out hydrogenation reaction in the 3rd hydrogenation reactor 3, and reaction pressure 1.5~
4.0MPaG, 145~285 DEG C of reaction temperature, catalyst system is Cu/SiO2, react for gas phase fast reaction, the reaction time 1~
10s.Ethylene glycol in 3rd hydrogenation reactor 3 leaves the flow detector on the 3rd hydrogenation reactor 3, outlet from outlet
Detected, hydrogen make device is to being passed through hydrogen make-up in the pipeline of dimethyl oxalate and hydrogen mixed gas.3rd hydrogenation is anti-
Device 3 is answered at least to produce 100,000 tons of ethylene glycol every year.
In step 2, the steam produced in the first hydrogenation reactor 1 or the second hydrogenation reactor 2 enters air pressure balancer 4
In, the ethylene glycol of pressure reduction is back in the first hydrogenation reactor 1 or the second hydrogenation reactor 2, and some vapor is expelled to outer
Portion, unreacted hydrogen is passed through into hydrogen circulation pipe.In step 3, in the first hydrogenation reactor 1 or the second hydrogenation reactor 2
The steam of generation enters in air pressure balancer 4, and the ethylene glycol of pressure reduction is back to the first hydrogenation reactor 1 or the second hydrogenation is anti-
Answer in device 2, some vapor is expelled to outside, unreacted hydrogen is passed through into hydrogen circulation pipe.The steam of discharge can be passed through to
In steam collection portion, during the pressure of the steam of discharge is 0.5MPa (G), step 4, the amount of filling into of hydrogen is ethylene glycol per ton benefit
Fill 1500~1800Nm3Hydrogen.MPa (G) represents meter pressure, Nm3Refer to the gas body in 0 degree Celsius of 1 normal atmosphere pressure
Product, is known technology.
Operation principle:Hydrogen is blended in the first hydrogenation reactor or the second hydrogenation reactor with dimethyl oxalate to be occurred to add
Hydrogen react, reacted product enter the 3rd hydrogenation reactor in carries out hydrogenation reaction, due to the 3rd hydrogenation reactor volume compared with
Greatly, large-scale production can be met to require, and the first hydrogenation reactor and the second hydrogenation reactor do not stop switching and used, therefore catalysis
Agent heating is not obvious, is difficult coking on the inwall of reactor, keeps catalyst activity, and cleaning is also more convenient.
Claims (6)
1. a kind of device of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol, it is characterised in that:The first hydrogenation including being arranged in parallel is anti-
Answer device (1) and the second hydrogenation reactor (2), air pressure balancer (4), the 3rd hydrogenation reactor (3), first hydrogenation reactor
(1) it is connected respectively with the pipeline (5) of dimethyl oxalate and hydrogen mixed gas can be passed through with the air inlet of the second hydrogenation reactor (2)
It is logical, selection is provided with the pipeline (5) gaseous mixture is passed through the first hydrogenation reactor (1) or the second hydrogenation reactor (2)
Reversal valve, first hydrogenation reactor (1) and the outlet of the second hydrogenation reactor (2) and entering for the 3rd hydrogenation reactor (3)
Mouth is connected, and the outlet of the 3rd hydrogenation reactor (3) is connected with ethylene glycol collection portion, first hydrogenation reactor
(1), the second hydrogenation reactor (2), the 3rd hydrogenation reactor (3) is connected with air pressure balancer (4) respectively.
2. device according to claim 1, it is characterised in that:First hydrogenation reactor (1), the second hydrogenation reactor
(2) again or it is provided with the compound reactor of tubulation and dividing plate for shell and tube reactor or plate-type reactor.
3. device according to claim 2, it is characterised in that:When the first hydrogenation reactor (1), the second hydrogenation reactor
(2) when being shell and tube reactor or compound reactor, in first hydrogenation reactor (1), the second hydrogenation reactor (2)
Tubulation length is 1~3m.
4. device according to claim 1, it is characterised in that:3rd hydrogenation reactor (3) for be provided with tubulation with
The compound reactor of dividing plate.
5. device according to claim 4, it is characterised in that:The volume of 3rd hydrogenation reactor (3) is more than first
The volume of hydrogenation reactor (1) or the second hydrogenation reactor (2).
6. according to any described device of claims 1 to 3, it is characterised in that:First hydrogenation reactor (1), second add
Pressure sensor is provided with hydrogen reactor (2), the 3rd hydrogenation reactor (3), temperature sensor, first hydrogenation reaction
Device (1), the second hydrogenation reactor (2), the 3rd hydrogenation reactor (3) and the pipeline of dimethyl oxalate and hydrogen mixed gas can be passed through
On be provided with flow detector.
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CN112142560A (en) * | 2020-10-20 | 2020-12-29 | 宁波中科远东催化工程技术有限公司 | Oxalate hydrogenation system and method |
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