CN109482107A - The gasification method and vapourizing unit of dimethyl oxalate - Google Patents
The gasification method and vapourizing unit of dimethyl oxalate Download PDFInfo
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- CN109482107A CN109482107A CN201811450535.3A CN201811450535A CN109482107A CN 109482107 A CN109482107 A CN 109482107A CN 201811450535 A CN201811450535 A CN 201811450535A CN 109482107 A CN109482107 A CN 109482107A
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Abstract
The present invention discloses a kind of gasification method of dimethyl oxalate, includes the following steps: that (1), DMO fresh feed and DMO recycle stock are fed by being mixed to form DMO, is vaporized after the DMO charging is preheated into vaporization tower；2), total hydrogen feed is divided into two strands of materials, and first burst of hydrogen charging does not enter the vaporization tower, and second burst of hydrogen charging enters from the tower bottom of the vaporization tower, and the DMO after vaporization is taken out of from the top of the vaporization tower, then mixes with first burst of hydrogen charging；The gasification method of dimethyl oxalate of the invention, the impurity content significantly reduced from the mixed gas discharging that vaporization tower comes out greatly improve production efficiency, reduce production cost so that the cycle of operation of packing layer and catalyst significantly extends.The invention also discloses the vapourizing units of the dimethyl oxalate of the gasification method based on above-mentioned dimethyl oxalate.
Description
Technical field
The invention belongs to chemical technology fields more particularly to coal based synthetic gas to prepare ethylene glycol technique dimethyl oxalate in preparation
Vaporescence, and in particular to the gasification method and vapourizing unit of dimethyl oxalate.
Background technique
Ethylene glycol (EG) is a kind of important industrial chemicals, mainly for the production of polyester fiber, polyester plastics, antifreezing agent,
Lubricant, plasticizer, explosive and chemical industry intermediate product.The process route of EG is synthesized, mainly includes petroleum path, coal EG route
And biomass EG route, accounting at present leading is still petroleum path, i.e. epoxyethane water is legal.With petroleum resources
Worsening shortages carry out the C1 chemical industry based on natural gas and coal-based feedstocks and have important practical significance to China, the relevant technologies
Also quick development is achieved in the nineties in last century.Wherein, the CO and nitrous acid ester gas phase catalysis that coal goes out through gasification separation are closed
It is rapidly developed at the technology of dimethyl oxalate (DMO) and mature, and opens the non-petroleum way for adding hydrogen preparing ethylene glycol (EG) by DMO
Diameter.
In the technique of hydrogenation of dimethyl oxalate to synthesizing ethylene glycol, dimethyl oxalate raw material is liquid, and the reaction used
Type formula be gas-solid catalyst reactor, therefore, it is necessary to be arranged DMO vaporization tower with after the dimethyl oxalate feed vaporization by liquid again
It is reacted with hydrogen mixing.
In the prior art, it after DMO charging is preheated to certain temperature, is atomized in vaporization tower using special nozzle,
The hydrogen entered by the tower bottom of vaporization tower further heats the DMO after atomization, and makes its vaporization, then hydrogen and gaseous
The mixed airflow of DMO comes out from the tower top of vaporization tower, then is heated to temperature required for hydrogenation reaction as heater, finally enters
Hydrogenation catalyst reactor carries out catalytic hydrogenation reaction to prepare ethylene glycol.Entrainment phenomenon is very in the technique, in vaporization tower
Seriously, DMO raw material is easily carried secretly by hydrogen to the upper layer filler of vaporization tower, or even is further taken vaporization tower out of and entered catalytic hydrogenation
The catalyst bed of reactor, and the impurity in DMO at the operational easy coking and block the filler in vaporization tower and catalysis
Catalyst bed in hydrogenator causes the resistance of vaporization tower and catalyst bed to increase, leads to hydrogenation reaction system
The cycle of operation is short.
Therefore, it is necessary to be improved to the gasification method of existing dimethyl oxalate, to overcome in the prior art
State technological deficiency.
Summary of the invention
The first purpose of the invention is to provide a kind of gasification methods of dimethyl oxalate, are existed in the prior art with overcoming
Drawbacks described above.It was found by the inventors of the present invention that according to the technical solution of the present invention, can be effectively reduced vaporization tower and hydrogen added to urge
The cycle of operation of the pressure drop of change reactor, packing layer and catalyst significantly extends, so that the cycle of operation of ethylene glycol process units
Extend, greatly improves production efficiency, reduce production cost.
It is technical solution of the present invention below:
The gasification method of dimethyl oxalate, includes the following steps:
(1), by being mixed to form DMO charging, the DMO charging is preheated laggard for DMO fresh feed and DMO recycle stock
Enter vaporization tower to be vaporized；
(2), total hydrogen feed is divided into two strands of materials, and first burst of hydrogen charging does not enter the vaporization tower, second strand of hydrogen
Charging enters from the tower bottom of the vaporization tower, and the DMO after vaporization is taken out of from the top of the vaporization tower, then with first strand of hydrogen
Gas charging mixing；
Wherein: in the step (1), the recycle ratio of the DMO fresh feed and DMO recycle stock is 10.9~22；Institute
It states in step (2), the gas liquid ratio in the vaporization tower is 11~17；Into second strand of hydrogen charging in the vaporization tower
Temperature be higher than enter the vaporization tower in the DMO charging temperature.
According to the present invention, the total hydrogen feed and the hydrogen ester molar ratio of DMO fresh feed are controlled 50~100.
Preferably, the recycle ratio of the DMO fresh feed and DMO recycle stock is 12.4~22.
It is further preferred that the recycle ratio of the DMO fresh feed and DMO recycle stock is 12.9~22, the vaporization
Gas liquid ratio in tower is 14~17.
According to the present invention, the volume flow of second strand of hydrogen charging be the volume flow of total hydrogen feed 13%~
60%.
According to the present invention, 160~190 DEG C are preheated into the DMO charging of the vaporization tower；Into the vaporization
Second strand of hydrogen charging of tower is preheated to 180 DEG C~210 DEG C.
Preferably, the total hydrogen feed is preheated to 180 DEG C~210 DEG C.
According to the present invention, the vaporization tower is packed tower, upper layer and lower layer filler is arranged in tower, the DMO charging is at two layers
Enter the vaporization tower between filler.
According to the present invention, the wire feeding of the packed tower is selected from Raschig ring, Pall ring, cascade ring, berl saddle, square saddle
Filler or metal ring intalox.
According to the present invention, the corresponding number of theoretical plate of packed height needed for the vaporization tower is 1~10 piece, and operating pressure is
1~5Mpa.
Preferably, the corresponding number of theoretical plate of packed height needed for the vaporization tower is 5~10 pieces.
According to the present invention, the DMO fresh feed and DMO recycle stock enter vaporization tower progress adiabatic vaporization.Institute
Heat needed for the adiabatic vaporization stated refers to the DMO charging heating vaporization into the vaporization tower, completely by entering
The heat of second strand of hydrogen charging in the vaporization tower provides, and does not provide external heat source.
Certainly, the vaporization tower can also further provide for external heating, to ensure the DMO charging in the vaporization tower
It is interior to be smoothly vaporized, such as: tower reactor reboiler is provided, or increases heating dish at the middle part of vaporization tower.When due to can not
Control factor, the temperature for causing second strand of hydrogen charging to enter vaporization tower is inadequate, and then leads to the heat for vaporizing the DMO charging
Amount is inadequate.At this point, can be by providing external heating, to ensure that the DMO charging can be smoothly vaporized in the vaporization tower.
Using the production method for the ethylene glycol that the gasification method of above-mentioned dimethyl oxalate is vaporized, vapour is essentially eliminated
The coking phenomenon for changing inner-tower filling material layer and hydrogenation catalyst catalyst reactor bed, effectively reduces vaporization tower upper packing layers
And the pressure drop of hydrogenation catalyst reactor, so that the cycle of operation of packing layer and catalyst significantly extends, while maintaining and adding hydrogen anti-
Required hydrogen ester ratio is answered, and then has ensured the operation steady in a long-term of ethylene glycol process units, greatly improves production efficiency, is dropped
Low production cost.
Second object of the present invention is, provides a kind of vapourizing unit of dimethyl oxalate, including DMO charging mixing dress
Set, DMO circulating pump, DMO preheater, vaporization tower, hydrogen preheater and add hydrogen entry mixers；
One end of DMO fresh feed pipe and DMO circulation pipe is respectively connected to the DMO charging mixing arrangement, DMO circulation pipe
The other end connect with the tower reactor of the vaporization tower, the lower part discharge port of one end of DMO feed pipe and the DMO entry mixers
Connection, the other end are connect with the middle part feed inlet of the vaporization tower, and the middle part feed inlet of the vaporization tower is connected with liquid distribution
Device is provided with DMO circulating pump and DMO preheater on the DMO feed pipe；
The top of the vaporization tower is connected with mixed gas discharge nozzle, and the hydrogen is arranged on the total hydrogen feed pipeline
Preheater, the total hydrogen feed pipeline further include the first hydrogen feed tube and the second hydrogen feed tube, the first hydrogen feed tube
Described plus hydrogen entry mixers are respectively connected to the mixed gas discharge nozzle, the second hydrogen mixing tube is connected to described
The tower reactor of vaporization tower.
According to the present invention, the DMO charging mixing arrangement can be conventional in the prior art mixer or blending tank.
Preferably, the DMO charging mixing arrangement is DMO circulating storage groove.
The DMO circulating storage groove is also connected with DMO discharge line, can according to the impurity content in the DMO circulating storage groove,
The DMO material of a certain amount of higher impurities is intermittently or continuously given off into reaction system from the DMO circulating storage groove.From
And it is further ensured that the impurity into vaporization tower and follow-up hydrogenation catalytic reactor is few, improve making for packing layer and hydrogenation catalyst
With the service life, the pressure drop of vaporization tower and hydrogenation catalyst reactor is reduced, ensures the operation steady in a long-term of ethylene glycol process units, is improved
Production efficiency reduces production cost.
Certainly, the impurity content that also can detect the DMO in the tower reactor of the vaporization tower, intermittently or continuously will be a certain amount of
DMO material gives off reaction system from the tower reactor of the vaporization tower.It is acted on contains with the higher impurity of above-mentioned DMO circulating storage groove discharge
The DMO material of amount be it is identical, this will not be repeated here.
According to the present invention, the vaporization tower further includes tower reactor reboiler.The tower reactor reboiler can provide external heat source, really
Protect the vaporization of the DMO charging.
According to the present invention, the vaporization tower further includes heating dish.The tower reactor reboiler can provide external heat source, it is ensured that institute
State the vaporization of DMO charging.
Compared with prior art, the present invention has following advantageous effects:
The gasification method of dimethyl oxalate of the invention combines DMO new by the gas liquid ratio in optimization vaporization tower, and effectively
The recycle ratio and other technological factors of fresh charging and DMO recycle stock, effectively reduce the gaseous mixture come out from vaporization tower top
Impurity content in body discharging, essentially eliminates the coking of packing layer and hydrogenation catalyst catalyst reactor bed in vaporization tower
Phenomenon significantly reduces the pressure drop of vaporization tower and hydrogenation catalyst reactor, so that the cycle of operation of packing layer and catalyst is significant
Extend, while hydrogen ester molar ratio needed for maintaining hydrogenation reaction, and then has ensured the fortune steady in a long-term of ethylene glycol process units
Row, greatly improves production efficiency, reduces production cost.
Detailed description of the invention
Fig. 1 is the vaporization flow chart of the dimethyl oxalate of the embodiment of the present invention 1-9.
Fig. 2 is the vaporization flow chart of the dimethyl oxalate of comparative example 1.
In figure: T101- vaporization tower, V101-DMO circulating storage groove, (H101, H102)-preheater, SP101- Hydrogen Separation
Device, M101- add hydrogen entry mixers
Specific embodiment
Below in conjunction with specific embodiment, the invention will be further described.It should be understood that following embodiment is merely to illustrate this
Invention is not for limiting the scope of the invention.
Fig. 1 is the vaporization flow chart of dimethyl oxalate in preparation of ethanediol by dimethyl oxalate hydrogenation technique of the invention.Tool
Body technology process is described as follows:
The DMO recycle stock S109 that DMO fresh feed S101 and vaporization tower T101 tower bottom come out respectively enters DMO circulation storage
Slot V101.The ratio between the flow of DMO recycle stock and the flow of DMO fresh feed are defined as recycle ratio, in following embodiment, is recycled
Than being 10.9~22.
The DMO charging S106 flowed out from DMO circulating storage groove V101 is sent to preheater H101 and is preheated to 160 DEG C~190 DEG C,
Among two layers of filler that DMO charging S107 after preheating then enters vaporization tower T101 with liquid form, pass through liquid point
Cloth device is sprayed；The preheated device H102 of total hydrogen feed S102 is preheated to 180 DEG C~210 DEG C, total hydrogen after being preheated
Gas feeds S103.
According to heat needed for vaporization DMO charging S107, total hydrogen feed S103 is by hydrogen gas segregator SP101 by certain
Ratio is divided into two bursts of chargings, and first gang of hydrogen charging S104 does not enter vaporization tower, second gang of hydrogen charging S105 then from tower reactor into
Enter vaporization tower T101, second strand of hydrogen charging S105 and DMO charging S107 gas-liquid two-phase carries out caloic friendship in vaporization tower T101
It changes, DMO feeds S107 and vaporized in vaporization tower T101 by second burst of hydrogen charging S105 heating, in tower top by second strand of hydrogen
Charging S105 takes vaporization tower T101, mixed gas discharging S108 and the first strand of hydrogen charging S104 for not entering vaporization tower T101 out of
It is mixed adding in hydrogen entry mixers M101, is formed plus hydrogen feeds S110, be then warming up to temperature required for hydrogenation reaction, with
Enter hydrogenator afterwards.
Unboiled DMO recycle stock S109 enters DMO circulating storage groove V101, while basis by tower bottom in vaporization tower T101
The impurity content in the DMO in circulating storage groove V101 detected, discharge a small amount of liquid phase DMO material S111 DMO to be fed in
Impurity concentration maintain lower level.
In the following example, the flow of total hydrogen feed S102 and the flow of DMO fresh feed S101 are according to hydrogenation reaction
Required hydrogen ester molar ratio (referred to as hydrogen ester ratio) is set as 50~100.The stream of S105 can be fed by adjusting second strand of hydrogen
Heat of vaporization needed for guaranteeing to vaporize DMO charging S107 is measured with the heating load of preheater H101.
In the following example, vaporization tower T101 is packed tower, and upper layer and lower layer filler: upper packing layers and lower part is arranged in tower
The DMO charging S107 of packing layer, liquid carries out spray charging, lower part packing layer by liquid distribution trough in the centre of two layers of filler
The flow channel of dispersion is provided for gas liquid two-phase flow, plays the uniformly distributed effect of gas-liquid, and provide largely for gas-liquid two-phase
Contact surface is conducive to the vaporescence of DMO to promote the Mass and heat transfer of gas-liquid two-phase.Upper packing layers, which then play, to disappear
Except the effect of entrainment.Selectable filler in packed column type has Raschig ring, Pall ring, cascade ring, berl saddle, square saddle to fill out
Material or metal ring intalox.
According to calculating, in operable range, the corresponding number of theoretical plate of packed height needed for vaporization tower is 1~10
Block, operating pressure are 1~5Mpa.The operation gas liquid ratio of vaporization tower is 11~17.
Technical solution of the present invention is illustrated below by way of specific embodiment.Described in following exemplary embodiment
Embodiment do not represent all embodiments consistent with the application.On the contrary, they are only and such as appended claims
The example of the consistent method or apparatus of some aspects be described in detail in book, the application.
The gasification method of 1 dimethyl oxalate of embodiment
The process flow of the present embodiment is as shown in Figure 1, concrete technology flow process is described as follows:
The DMO recycle stock S109 that DMO fresh feed S101 and vaporization tower T101 tower bottom come out respectively enters DMO circulation storage
Slot V101 mixing, recycle ratio 18.8.It is pre- that the DMO charging S106 flowed out from DMO circulating storage groove V101 is sent to preheater H101
Heat is to 160 DEG C, among two layers of filler that the DMO charging S107 after preheating then enters vaporization tower T101 with liquid form,
It is sprayed by liquid distribution trough.
The preheated device H102 of total hydrogen feed S102 is preheated to 180 DEG C, the total hydrogen feed S103 after being preheated, control
Hydrogen manufacturing ester ratio is 50.According to heat needed for vaporization DMO charging S107, total hydrogen feed S103 passes through hydrogen gas segregator SP101
It is divided into two bursts of chargings, first gang of hydrogen charging S104 does not enter vaporization tower, and second gang of hydrogen charging S105 then enters vapour from tower reactor
Change tower T101, controls the 60% of the volume flow that the volume flow that second strand of hydrogen is fed is total hydrogen feed.Second strand
Hydrogen charging S105 and DMO charging S107 gas-liquid two-phase carries out caloic exchange in vaporization tower T101, controls the gas in vaporization tower
Liquor ratio is that 17, DMO charging S107 is vaporized in vaporization tower T101 by the charging S105 heating of second strand of hydrogen, then from tower top by the
Two gangs of hydrogen charging S105 take vaporization tower T101, mixed gas discharging S108 and first strand of hydrogen for not entering vaporization tower T101 out of
Charging S104 is mixed adding in hydrogen entry mixers M101, forms hydrogenation catalyst reactor feed S110, is then warming up to plus hydrogen
Temperature required for reacting, subsequently enters hydrogenator.
In vaporization tower T101 unboiled DMO recycle stock S109 enters V101 by tower bottom, while according to detecting
The impurity content in DMO in V101 is discharged the DMO material S111 of a small amount of liquid phase and is maintained with the impurity concentration in feeding DMO
In lower level.
In the present embodiment, 1 piece of the corresponding number of theoretical plate of packed height needed for controlling vaporization tower, the operating pressure of vaporization tower
For 1Mpa.
The gasification method of 2 dimethyl oxalate of embodiment
Flow chart is same as Example 1, and difference is:
The recycle ratio for controlling DMO fresh feed and DMO recycle stock is 12.9.
DMO charging S106 is sent to preheater H101 and is preheated to 180 DEG C.
The preheated device H102 of total hydrogen feed S102 is preheated to 200 DEG C.
The 34% of the volume flow that the volume flow for controlling second strand of hydrogen charging S105 is total hydrogen feed S102.
Controlling the operation gas liquid ratio in vaporization tower T101 is 14.
1 piece of the corresponding number of theoretical plate of packed height needed for controlling vaporization tower, the operating pressure of vaporization tower are 3Mpa.
The gasification method of 3 dimethyl oxalate of embodiment
Flow chart is same as Example 1, and difference is:
The recycle ratio for controlling DMO fresh feed and DMO recycle stock is 10.9.
DMO charging S106 is sent to preheater H101 and is preheated to 190 DEG C.
The preheated device H102 of total hydrogen feed S102 is preheated to 210 DEG C.
The 26% of the volume flow that the volume flow for controlling second strand of hydrogen charging S105 is total hydrogen feed S102.
Controlling the operation gas liquid ratio in vaporization tower T101 is 13.
1 piece of the corresponding number of theoretical plate of packed height needed for controlling vaporization tower, the operating pressure of vaporization tower are 5Mpa.
The gasification method of 4 dimethyl oxalate of embodiment
Flow chart is same as Example 1, and difference is:
The recycle ratio for controlling DMO fresh feed and DMO recycle stock is 22.
The 37% of the volume flow that the volume flow for controlling second strand of hydrogen charging S105 is total hydrogen feed S102.
Controlling the operation gas liquid ratio in vaporization tower is 14.
Controlling hydrogen ester ratio is 80.
5 pieces of the corresponding number of theoretical plate of packed height needed for controlling vaporization tower, the operating pressure of vaporization tower are 1Mpa.
The gasification method of 5 dimethyl oxalate of embodiment
Flow chart is same as Example 1, and difference is:
The recycle ratio for controlling DMO fresh feed and DMO recycle stock is 14.5.
DMO charging S106 is sent to preheater H101 and is preheated to 180 DEG C.
The preheated device H102 of total hydrogen feed S102 is preheated to 200 DEG C.
The 21% of the volume flow that the volume flow for controlling second strand of hydrogen charging S105 is total hydrogen feed S102.
Controlling the operation gas liquid ratio in vaporization tower is 12.
Controlling hydrogen ester ratio is 80.
5 pieces of the corresponding number of theoretical plate of packed height needed for controlling vaporization tower, the operating pressure of vaporization tower are 3Mpa.
The gasification method of 6 dimethyl oxalate of embodiment
Flow chart is same as Example 1, and difference is:
The recycle ratio for controlling DMO fresh feed and DMO recycle stock is 12.4.
DMO charging S106 is sent to preheater H101 and is preheated to 190 DEG C.
The preheated device H102 of total hydrogen feed S102 is preheated to 210 DEG C.
The 16% of the volume flow that the volume flow for controlling second strand of hydrogen charging S105 is total hydrogen feed S102.
Controlling the operation gas liquid ratio in vaporization tower is 11.
Controlling hydrogen ester ratio is 80.
5 pieces of the corresponding number of theoretical plate of packed height needed for controlling vaporization tower, the operating pressure of vaporization tower are 5Mpa.
The gasification method of 7 dimethyl oxalate of embodiment
Flow chart is same as Example 1, and difference is:
The recycle ratio for controlling DMO fresh feed and DMO recycle stock is 19.
The 30% of the volume flow that the volume flow for controlling second strand of hydrogen charging S105 is total hydrogen feed S102.
Controlling the operation gas liquid ratio in vaporization tower is 16.
Controlling hydrogen ester ratio is 100.
10 pieces of the corresponding number of theoretical plate of packed height needed for controlling vaporization tower, the operating pressure of vaporization tower are 1Mpa.
The gasification method of 8 dimethyl oxalate of embodiment
Flow chart is same as Example 1, and difference is:
The recycle ratio for controlling DMO fresh feed and DMO recycle stock is 12.9.
DMO charging S106 is sent to preheater H101 and is preheated to 180 DEG C.
The preheated device H102 of total hydrogen feed S102 is preheated to 200 DEG C.
The 17% of the volume flow that the volume flow for controlling second strand of hydrogen charging S105 is total hydrogen feed S102.
Controlling the operation gas liquid ratio in vaporization tower is 14.
Controlling hydrogen ester ratio is 100.
10 pieces of the corresponding number of theoretical plate of packed height needed for controlling vaporization tower, the operating pressure of vaporization tower are 3Mpa.
The gasification method of 9 dimethyl oxalate of embodiment
Flow chart is same as Example 1, and difference is:
The recycle ratio for controlling DMO fresh feed and DMO recycle stock is 10.9.
DMO charging S106 is sent to preheater H101 and is preheated to 190 DEG C.
The preheated device H102 of total hydrogen feed S102 is preheated to 210 DEG C.
The 13% of the volume flow that the volume flow for controlling second strand of hydrogen charging S105 is total hydrogen feed S102.
Controlling the operation gas liquid ratio in vaporization tower is 13.
Controlling hydrogen ester ratio is 100.
10 pieces of the corresponding number of theoretical plate of packed height needed for controlling vaporization tower, the operating pressure of vaporization tower are 5Mpa.
The gasification method of 1 dimethyl oxalate of comparative example
The technological parameter of comparative example 1 is substantially the same manner as Example 2, control total hydrogen feed S102 and DMO fresh feed
The hydrogen ester ratio of S101 is 50, and the corresponding number of theoretical plate of packed height needed for controlling vaporization tower is 1 piece, the operating pressure of vaporization tower
For 3Mpa.Process flow chart is as shown in Fig. 2, difference is:
After DMO fresh feed S101 is preheated to 180 DEG C, from two layers of filler intermediate feed of the vaporization tower T101, make
It is atomized in vaporization tower T101 with atomizer.Total hydrogen feed is preheated to 200 DEG C, then enters the vaporization by tower bottom
DMO after atomization is further fed heating, and makes its vaporization by tower T101, and then the mixed gas of hydrogen and gaseous DMO go out
Material comes out from the tower top of the vaporization tower T101, then is heated to temperature required for hydrogenation reaction as heater, finally enters and adds
Hydrogen catalysis reactor carries out catalytic hydrogenation reaction to prepare ethylene glycol.
In the present embodiment, the operation gas liquid ratio in the vaporization tower T101 is 41.
The method of embodiment 11-20 dimethyl oxalate production ethylene glycol
Embodiment 11-20 respectively corresponds the gasification method of the dimethyl oxalate using comparative example 1 and embodiment 1-9 to oxalic acid
Dimethyl ester is vaporized, and obtains plus hydrogen feeds S110, hydrogen charging S110 is added to be heated to 200 DEG C of hydrogenation reaction temperature by heater
Afterwards, it is reacted, while is detected before vaporization tower T101 to this section apparatus after hydrogenation catalyst reactor into hydrogenator
Overall presure drop.The results are shown in Table 1 for embodiment.
The evaluation of the method for 1 embodiment 1-9 of table and comparative example 1
It can be seen from the data of table 1 in the process of dimethyl oxalate production ethylene glycol, with days running
Increase, the overall presure drop of comparative example 1 steeply rises, and when running to 180 days, compared with when running 30 days, overall presure drop increases
320%；When running to 360 days, compared with when running 30 days, overall presure drop increases by 677%.It can be seen that using existing oxalic acid diformazan
The gasification method of ester carries out ethylene glycol production, and overall presure drop steeply rises with the increase of days running.
And the embodiment 12-20 of the gasification method of embodiment 1-9 is used, when running 180 days, with 30 days phases of operation
Than overall presure drop increases by 3~10.9%；When running to 360 days, compared with when running 30 days, overall presure drop increases by 5~20%.By
This as it can be seen that dimethyl oxalate production ethylene glycol process in, using the gasification method of dimethyl oxalate of the invention, always
The increase of pressure drop is substantially reduced.Especially for embodiment 18-20, when running 180 days, compared with when running 30 days, stagnation pressure
Drop increases by 3~5.7%；When running to 360 days, compared with when running 30 days, overall presure drop increases by 5~8.4%, the increasing of overall presure drop
Add minimum.At this point, the corresponding number of theoretical plate of packed height needed for vaporization tower is 5~10 pieces, operating pressure is 1~5Mpa, behaviour
Making gas liquid ratio is 13~17, and recycle ratio is 10.9~19.
Meanwhile after operation 180 days, reacted using the filler and hydrogenation catalyst of the vaporization tower of the gasification method of comparative example 1
Catalyst in device is required to replace, and the vaporizer tower and hydrogenation catalyst reactor that use the gasification method of embodiment 1-9 are then
No replacement is required filler and catalyst, the upper packing layers and the catalyst layer in hydrogenation catalyst reactor that vaporization tower can be observed
Coking phenomenon greatly reduces, and can operate normally 360 days or more, and the cycle of operation of vaporizer tower and hydrogenation catalyst reactor is obvious
It improves.
Specific embodiments of the present invention are described in detail above, but it is only used as example, the present invention is not intended to limit
In particular embodiments described above.To those skilled in the art, it any equivalent modifications to the practical progress and replaces
In generation, is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equal transformation and repair
Change, all should be contained within the scope of the invention.
Claims (10)
1. the gasification method of dimethyl oxalate, which comprises the steps of:
(1), DMO fresh feed and DMO recycle stock enter vapour after the DMO charging is preheated by being mixed to form DMO charging
Change tower to be vaporized；
(2), total hydrogen feed is divided into two strands of materials, and first burst of hydrogen charging does not enter the vaporization tower, second burst of hydrogen charging
Enter from the tower bottom of the vaporization tower, and the DMO after vaporization taken out of from the top of the vaporization tower, then with first strand of hydrogen into
Material mixing；
Wherein: in the step (1), the recycle ratio of the DMO fresh feed and DMO recycle stock is 10.9~22；The step
Suddenly in (2), the gas liquid ratio in the vaporization tower is 11~17；Into the temperature of second strand of hydrogen charging in the vaporization tower
Degree is higher than the temperature of the DMO charging entered in the vaporization tower.
2. the gasification method of dimethyl oxalate according to claim 1, which is characterized in that the total hydrogen feed and DMO
The hydrogen ester molar ratio of fresh feed is controlled 50~100.
3. the gasification method of dimethyl oxalate according to claim 1, which is characterized in that the DMO fresh feed and DMO
The recycle ratio of recycle stock is 12.4~22.
4. the gasification method of dimethyl oxalate according to claim 1, which is characterized in that second strand of hydrogen charging
Volume flow is the 13%~60% of the volume flow of total hydrogen feed.
5. the gasification method of dimethyl oxalate according to claim 1, which is characterized in that enter the described of the vaporization tower
DMO charging is preheated to 160~190 DEG C；Into the vaporization tower second strand of hydrogen charging be preheated to 180 DEG C~
210℃。
6. the gasification method of dimethyl oxalate according to claim 1, which is characterized in that the vaporization tower is packed tower,
Upper layer and lower layer filler is set in tower, and the DMO charging enters the vaporization tower between two layers of filler.
7. the gasification method of dimethyl oxalate according to claim 1, which is characterized in that filler needed for the vaporization tower
Highly corresponding number of theoretical plate is 1~10 piece, and the operating pressure of the vaporization tower is 1~5Mpa.
8. the gasification method of dimethyl oxalate according to claim 7, which is characterized in that filler needed for the vaporization tower
Highly corresponding number of theoretical plate is 5~10 pieces.
9. the gasification method of dimethyl oxalate according to claim 1 to 8, which is characterized in that the DMO is new
Fresh charging and DMO recycle stock enter the vaporization tower and carry out adiabatic vaporization.
10. the vapourizing unit of dimethyl oxalate, which is characterized in that including DMO charging mixing arrangement, DMO circulating pump, DMO preheating
Device, vaporization tower, hydrogen preheater and plus hydrogen entry mixers；
One end of DMO fresh feed pipe and DMO circulation pipe is respectively connected to DMO charging mixing arrangement, DMO circulation pipe it is another
One end is connect with the tower reactor of the vaporization tower, and the lower part discharge port of one end of DMO feed pipe and DMO charging mixing arrangement connects
It connecing, the other end is connect with the middle part feed inlet of the vaporization tower, and the middle part feed inlet of the vaporization tower is connected with liquid distribution trough,
DMO circulating pump and DMO preheater are provided on the DMO feed pipe；
The top of the vaporization tower is connected with mixed gas discharge nozzle, and the hydrogen preheating is arranged on the total hydrogen feed pipeline
Device, the total hydrogen feed pipeline further include the first hydrogen feed tube and the second hydrogen feed tube, the first hydrogen feed tube and institute
It states mixed gas discharge nozzle and is respectively connected to described plus hydrogen entry mixers, the second hydrogen mixing tube is connected to the vaporization
The tower reactor of tower.
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| CN111454151A (en) * | 2020-04-26 | 2020-07-28 | 宁波中科远东催化工程技术有限公司 | Method for vaporizing dimethyl oxalate |
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