CN107673974A - The recycling method and device of a kind of nitrogen oxides - Google Patents
The recycling method and device of a kind of nitrogen oxides Download PDFInfo
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- CN107673974A CN107673974A CN201710854824.9A CN201710854824A CN107673974A CN 107673974 A CN107673974 A CN 107673974A CN 201710854824 A CN201710854824 A CN 201710854824A CN 107673974 A CN107673974 A CN 107673974A
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- nitrogen oxides
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- nitric acid
- recycling method
- ethylene glycol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/04—Preparation of esters of nitrous acid
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention provides a kind of recycling method of nitrogen oxides, aqueous solution of nitric acid haptoreaction in gas phase portion caused by ethylene glycol oxalate system and liquid phase part is formed into nitrogen oxides gas phase, the nitrogen oxides gas phase is circulated in ethylene glycol oxalate system.The present invention provides a kind of method of aqueous solution of nitric acid with the contact preparation nitrogen oxides of gas containing NO, and the nitrogen oxides includes NO, NO2、N2O3、N2O4Deng for maintaining the nitrogen oxides material equilibrium of ethylene glycol production oxalate system.Because reaction system is without methanol, improves operation temperature and be improved, and the high nitric acid conversion ratio thus brought, and safety problem caused by methyl nitrate caused by avoiding, realize safe and efficient target.
Description
Technical field
The present invention relates to a kind of compounds process for production thereof, more particularly to a kind of circulatory system of nitrogen oxides.
Background technology
In synthesis gas production ethylene glycol technique, oxalate system have lost part because by-product nitric acid and tail gas speed to put
Nitrogen oxides raw material is general using the method that NO is supplemented to system to keep system nitrogen oxides balance.NO passes through NH3Oxidation
Or obtained using natrium nitrosum with nitric acid reaction, NH3Method for oxidation NO industrially realize it is more difficult, and technique length investment
Greatly；And though natrium nitrosum is simple with nitric acid reaction NO reactions, the substantial amounts of sodium nitrate of by-product is, it is necessary to evaporate, crystallize, separate
Process, cost, high energy consumption.
In order to recycle oxalate system by-product nitric acid, patent CN1445208 discloses a kind of methyl nitrite that produces
Method, methyl nitrite, embodiment 1 are produced by the way that NO gases are contacted with the aqueous solution of methanol and nitric acid in tank reactor
~7 results show：Under the conditions of 0.2~0.4MPa of pressure, 28~50 DEG C of temperature, 1100~2100rpm of mixing speed, every liter anti-
The conversion rate for answering body product nitric acid is 1~31g/h；Under 50 DEG C of reaction temperatures, the conversion ratio of the nitric acid of embodiment 8 is
60.4wt%；Under 70 DEG C of reaction temperatures, the conversion ratio of the nitric acid of embodiment 9 is 79.6wt%.We can from embodiment data
To obtain, to make reactor outlet concentration of nitric acid drop to it is sufficiently low, when the timing for the treatment of capacity one is, it is necessary to increase reactor volume；
Though nitric acid conversion ratio, the present inventors' discovery when carrying out confirmatory experiment, the nitric acid containing methanol can be improved by improving reaction temperature
Water solution system, when reaction temperature is at 50~60 DEG C, detects that methyl nitrate is present in gas phase and liquid phase, work as reaction temperature
During more than 60 DEG C, methyl nitrate content improves rapid；Methyl nitrate is a kind of dangerous substance, is accumulated in systems, blast be present
Danger, therefore this method is uneconomical and not safe enough.
CN 104945262 discloses a kind of method of catalysis methanol reduction dust technology methyl nitrite, and patent uses carbon
Base catalyst, in fixed bed reactors, the conversion ratio of nitric acid is typically in more than 85wt%, to pursue high nitric acid conversion ratio, specially
Sharp method must use 5 mesh diameter above catalyst and more than 70 DEG C reaction temperatures.The problem of this method is present is catalyst
Particle diameter is small, and bed resistance is big, and operating cost is higher；Because reaction temperature is too high, methyl nitrate generation and thus band are equally existed
The safety issue come.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide a kind of recycling of nitrogen oxides
Method and apparatus, when maintaining the nitrogen oxides material equilibrium of ethylene glycol oxalate system in the prior art for solution, due to anti-
System is answered to bring safety problem and the problems such as nitric acid conversion ratio is low containing methanol and reaction temperature are too high.
In order to achieve the above objects and other related objects, the present invention is by being realized including following technical scheme.
The present invention provides a kind of recycling method of nitrogen oxides, by gas phase portion caused by ethylene glycol oxalate system
Nitrogen oxides gas phase is formed with the aqueous solution of nitric acid haptoreaction in liquid phase part, the nitrogen oxides gas phase is circulated for second two
In alcohol oxalate system.
The ethylene glycol oxalate system is prior art, and it includes oxonation device and esterification reaction tower, oxonation
Formed and circulated by pipeline communication between device and esterification reaction tower.The gas phase portion is by the gas in oxonation device out
Body.The liquid phase part is by the liquid in esterification reaction tower out.The nitrogen oxides gas phase, which enters in esterification reaction tower, to be followed
Ring uses.
Preferably, the gas phase portion is that synthesis gas produces the process gas circulated in ethylene glycol oxalate system.The gas
Mutually part is gas containing NO.It is highly preferred that the content of NO gases is 1~40vol% in the gas phase portion；Remaining is N2、CO2、
CH4, CO, the one or more in methyl nitrite.
The liquid phase part is that synthesis gas produces the mixing containing methanol, nitric acid and water caused by ethylene glycol oxalate system
Liquid.
Preferably, the methanol in the liquid phase part separates before haptoreaction removes.
Preferably, the liquid phase part is separated except methanol by methanol distillation column.The methanol distillation column is rectifying column,
Methanol is separated by rectification process.I.e. esterification column tower bottoms of the ethylene glycol oxalate system containing methanol, nitric acid and water returns through methanol
Tower, recovered overhead methanol are received, tower reactor obtains the aqueous solution containing nitric acid.Preferably, the methanol reclaimed in the methanol distillation column leads to
Piping enters esterification reaction tower, recycles.It is highly preferred that the methanol in the methanol distillation column passes through in esterification reaction tower
Portion enters.
The method according to the invention, the amount containing nitric acid is not limited in aqueous solution of nitric acid.Preferably, in aqueous solution of nitric acid
The mass ratio of nitric acid and water is less than 50wt%.
Preferably, the catalytic reaction temperature is 50~200 DEG C.It is highly preferred that catalytic reaction temperature
For 80~150 DEG C.
Preferably, the catalytic pressure is normal pressure~10barG.It is highly preferred that catalytic pressure be 2~
5barG。
Wherein reaction pressure selection is main considers that the conveying of gas/liquid material is convenient, when the inventive method is used for oxalate system
Nitrogen oxides material equilibrium when, preferable operating pressure is 2~5barG；Though improving Contact Temperature is advantageous to nitric acid conversion,
In view of energy consumption and running cost, preferable Contact Temperature is 80~150 DEG C.
Catalytic equipment is contact reactor, and it can use any consersion unit in the prior art.To improve nitre
Sour conversion ratio, in addition to improving reaction temperature, gas liquid contact is equally important, the method according to the invention, wherein nitric acid aqueous solution
Solution is contacted with gas containing NO and carried out preferably in the tower reactor for be advantageous to mass transfer, such as packed tower or is filled with catalysis
The fixed bed reactors of agent.Contact of the gas phase portion with liquid phase part can be with cocurrent, can also adverse current.
Preferably, haptoreaction is carried out in tower reactor.Preferably, the tower reactor is packed tower or dress
It is filled with the fixed bed reactors of catalyst.
Preferably, the filler in the packed tower can be one or both of random packing and structured packing.It is preferred that
Ground, the material of the filler is ceramics, stainless steel, Al2O3, the Al that is modified of activated carbon, NACF, Fe or Pt2O3, Fe or
One or more in the NACF that the activated carbon or Fe or Pt that Pt is modified are modified.
Preferably, the catalyst can use the Al that activated carbon, NACF, Fe or Pt are modified2O3, Fe or Pt be modified
One or more in the NACF that activated carbon or Fe or Pt are modified.
Preferably, the haptoreaction is also formed with liquid phase part, and the liquid phase part is discharged after gas-liquid separation, carries out
Wastewater treatment.The gas-liquid separator uses gas-liquid separator.
Preferably, product is cooled down before gas-liquid separation is carried out to catalytic product.Such as using heat exchange
Device cools down to product.
Preferably, the nitrogen oxides gas phase includes NO, NO2、N2O3、N2O4In one or more.
Nitrogen oxides caused by the haptoreaction is sent in ethylene glycol oxalate system, for maintaining the nitrogen oxygen of system
Compound material equilibrium.
Preferably, in order to improve nitrogen oxides gas phase quantum of output, nitric acid can also be added into the liquid phase after removal methanol
The aqueous solution.
As described above, the recycling method of the nitrogen oxides of the present invention, has the advantages that：
The present invention provides a kind of aqueous solution of nitric acid with the method for the contact preparation nitrogen oxides of gas containing NO, the nitrogen oxides
Include NO, NO2、N2O3、N2O4Deng for maintaining the nitrogen oxides material equilibrium of ethylene glycol production oxalate system.Due to reaction
Without methanol, raising operation temperature is improved system, and the high nitric acid conversion ratio thus brought, and avoids caused nitre
Safety problem caused by sour methyl esters, realize safe and efficient target.
Brief description of the drawings
Fig. 1 is to be applied to ethylene glycol oxalate system according to the inventive method to maintain the technique of nitrogen oxides material equilibrium
Schematic flow sheet.
Embodiment
Before the specific embodiment of the invention is further described, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiment；It is also understood that the term used in the embodiment of the present invention is specific specific in order to describe
Embodiment, the protection domain being not intended to be limiting of the invention.The test method of unreceipted actual conditions in the following example,
Generally according to normal condition, or the condition proposed by according to each manufacturer.
When embodiment provides number range, it should be appreciated that except non-invention is otherwise noted, two ends of each number range
Any one numerical value can be selected between point and two end points.Unless otherwise defined, in the present invention all technologies for using and
Scientific terminology is identical with the meaning that those skilled in the art of the present technique are generally understood that.Except used in embodiment specific method, equipment,
Outside material, according to grasp of the those skilled in the art to prior art and the record of the present invention, it can also use and this
Any method, equipment and the material of the similar or equivalent prior art of method, equipment described in inventive embodiments, material come real
The existing present invention.
In embodiment, the content of nitric acid is determined by ion chromatography, and other product assays are by infrared or gas-chromatography
Analysis determines.
Fig. 1 is to be applied to ethylene glycol oxalate system in the application to maintain the technological process of nitrogen oxides material equilibrium to show
It is intended to.As shown in figure 1, the equipment used in the technique include methanol distillation column 1, contact reactor 3, gas-liquid separator 5 with
And ethylene glycol oxalate system 6；Pass through pipeline communication, the methanol between the methanol distillation column 1 and the contact reactor 3
Liquid in recovery tower is entered in the contact reactor by pipeline；The contact reactor 3 and the gas-liquid separator 5 it
Between by pipeline communication, the reaction product in the contact reactor 3 is entered in the gas-liquid separator 5 by pipeline；It is described
By pipeline communication between gas-liquid separator 5 and the ethylene glycol oxalate system 6, the gas in the gas-liquid separator 5 leads to
Piping, which enters in the ethylene glycol oxalate system 6, to be recycled；The ethylene glycol oxalate system 6 and the haptoreaction
For device 3 by pipeline communication, the gas phase portion in the ethylene glycol oxalate system 6 enters the contact reactor 3 by pipeline
In；The ethylene glycol oxalate system 6 and the methanol distillation column 1 are by pipeline communication, in the ethylene glycol oxalate system 6
Liquid phase part by pipeline enter the methanol distillation column 1 in remove methanol.
The ethylene glycol oxalate system is prior art, and it includes oxonation device and esterification reaction tower, oxonation
Formed and circulated by pipeline communication between device and esterification reaction tower.The gas phase portion is by the gas in oxonation device out
Body.The liquid phase part is by the liquid in esterification reaction tower out.The nitrogen oxides gas phase, which enters in esterification reaction tower, to be followed
Ring uses.
Preferably, the pipeline between the methanol distillation column 1 and the contact reactor 3 is provided with pump.The pump 2 provides
Tower bottoms in methanol distillation column 1 is sent into the contact reactor 3 by pressure through piping.
Preferably, connected between the methanol distillation column 1 and the esterification reaction tower by pipeline, in methanol distillation column 1
Recovery methanol by pipeline enter the esterification reaction tower in.
Preferably, pipeline is provided with cooling device 4 between the contact reactor 3 and the gas-liquid separator 5.Institute
Condensing unit commonly used in the prior art, such as heat exchanger can be used by stating cooling device 4.Using cooling device to
The product that reaction is in contact in contact reactor 3 cools down processing before gas-liquid separation, beneficial to subsequent reactions and production
Thing processing.
Liquid phase containing methanol, nitric acid and water caused by ethylene glycol oxalate system 6 enters methanol distillation column 1 by pipeline
In, the methanol distillation column is rectifying column, and tower top obtains methanol, and is recycled in system, and tower reactor is obtained containing aqueous solution of nitric acid
Tower bottoms, by the Methanol Recovery separated；Recovery methanol enters in esterification reaction tower through pipeline to be continued to react；It is described
Tower bottoms enters in contact reactor 3 through pipeline, while the gas phase gas containing NO in ethylene glycol oxalate system 6 also enters through pipeline
Enter in the contact reactor 3, tower bottoms and gas phase gas containing NO haptoreaction in contact reactor 3, haptoreaction thing warp
Pipeline, which enters in gas-liquid separator 5, carries out gas-liquid separation, and the gas circulation of separation enters in the ethylene glycol oxalate system 6,
The liquid discharge of gas-liquid separation carries out wastewater treatment.
Catalytic equipment is contact reactor, and it can use any consersion unit in the prior art.To improve nitre
Sour conversion ratio, in addition to improving reaction temperature, gas liquid contact is equally important, the method according to the invention, wherein nitric acid aqueous solution
Solution is contacted with gas containing NO and carried out preferably in the tower reactor for be advantageous to mass transfer, such as packed tower or is filled with catalysis
The fixed bed reactors of agent.Contact of the gas phase portion with liquid phase part can be with cocurrent, can also adverse current.
Embodiment 1
Stainless steel helices tower, it is built-inStainless steel θ rings, the heat tape heating of reaction pipeline section, gas/liquid cocurrent
Operation；Liquid feedstock 40wt% containing nitric acid, remaining be water, flow 1.75L/h；Gas feed NO content 13vol%, CO contents
12vol%, remaining be N2, flow 2m3/h.110 DEG C of conversion zone temperature, pressure 5barG are controlled, bottom of towe sets cooling and gas-liquid separation
Device.After stablizing 1 hour, reaction product is analyzed, it is as a result as follows：Liquid phase flow 1.3kg/h, wherein containing H2O
81.9wt%, HNO36.7wt%, NO210.8wt%, other nitrogen oxides 0.4wt%；Gas phase flow rate 29.2L/min, wherein containing
H2O 2.4wt%, HNO30.4wt%, NO 10.5wt%, NO28.8wt%, other nitrogen oxides 0.4wt%；Nitric acid converts
Rate is 85wt%.Embodiment 2~7
In addition to liquid feedstock concentration of nitric acid, reaction temperature and pressure is changed, the other the same as in Example 1, as a result such as following table.
Embodiment 8
In addition to stainless steel helices is replaced with NACF, the other the same as in Example 1 is as a result as follows：Liquid phase flow 1.3kg/
H, wherein containing H2O 85.9wt%, HNO30.2wt%, NO213.1wt%, other nitrogen oxides 0.8wt%；Gas phase flow rate
29.3L/min, wherein containing H2O 2.4wt%, HNO30.01wt%, NO 10wt%, NO210.3wt%, other nitrogen oxides
0.4wt%；Nitric acid conversion ratio is 95wt%.
Embodiment 9
In addition to stainless steel helices is replaced with the Fe activated carbons being modified, the other the same as in Example 1, as a result nitric acid conversion ratio be
99.1wt%.
Embodiment 10
In addition to stainless steel helices is replaced with the Pt activated carbons being modified, the other the same as in Example 1, as a result nitric acid conversion ratio be
98.5wt%.
Embodiment 11
Solution containing methanol, nitric acid and water caused by esterification reaction tower in ethylene glycol oxalate system 6 enters by the road
Methanol distillation column, methanol distillation column are rectifying column, methanol distillation column recovered overhead methanol, reclaim methanol and are recycled to system by the road
In.46.3wt% containing nitric acid, water 53.1wt%, other 0.6wt% tower bottoms, by the road, tower reactor liquid pump and pipeline enter nitre
In acid/NO contact reactors 3, flow 350kg/h.The built-in activated carbon being modified with Pt of reactor.Ethylene glycol oxalate system carbonyl
Change process gas containing NO (NO content 13vol%, flow 20Nm caused by reactor3/ h) enter nitric acid/NO contacts by the road instead
Answer in device 3,150 DEG C of control conversion zone temperature, pressure 3barG, nitric acid/bottoms of NO contact reactors 3 by the road, heat exchanger
4 and pipeline enter gas-liquid separator 5 in, nitrogen-containing oxide gaseous stream is recycled to ethylene glycol by the road in gas-liquid separator 5
In the esterification reaction tower of oxalate system, for maintaining the nitrogen oxides material equilibrium of ethylene glycol oxalate system, gas-liquid separation
Device liquid phase stream carries out wastewater treatment by the road, wherein 0.2wt% containing nitric acid, nitric acid conversion ratio is 99.5wt%.
So the present invention effectively overcomes various shortcoming of the prior art and has high industrial utilization.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe
Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause
This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as
Into all equivalent modifications or change, should by the present invention claim be covered.
Claims (10)
- A kind of 1. recycling method of nitrogen oxides, by gas phase portion caused by ethylene glycol oxalate system and liquid phase part Aqueous solution of nitric acid haptoreaction form nitrogen oxides gas phase, the nitrogen oxides gas phase circulated for ethylene glycol oxalate system In.
- 2. the recycling method of nitrogen oxides according to claim 1, it is characterised in that：The gas phase portion is synthesis The process gas circulated in gas production ethylene glycol oxalate system.
- 3. the recycling method of nitrogen oxides according to claim 1, it is characterised in that：NO gas in the gas phase portion The content of body is 1~40vol%；Remaining is N2、CO2、CH4, CO, the one or more in methyl nitrite.
- 4. the recycling method of nitrogen oxides according to claim 1, it is characterised in that：The liquid phase part is synthesis Mixing liquid containing methanol, nitric acid and water caused by gas production ethylene glycol oxalate system.
- 5. the recycling method of nitrogen oxides according to claim 1, it is characterised in that：First in the liquid phase part Alcohol is separated before haptoreaction and removed.
- 6. the recycling method of nitrogen oxides according to claim 5, it is characterised in that：The liquid phase part passes through first Alcohol recovery tower is separated except methanol.
- 7. the recycling method of nitrogen oxides according to claim 1, it is characterised in that：The catalytic reaction Temperature is 50~200 DEG C.
- 8. the recycling method of nitrogen oxides according to claim 1, it is characterised in that：Catalytic pressure is 2 ~5barG.
- 9. the recycling method of nitrogen oxides according to claim 1, it is characterised in that：Including one in following feature Kind is a variety of：Catalytic equipment is tower reactor；The tower reactor is packed tower or the fixed bed reactors for being filled with catalyst；Filler in the packed tower can be one or both of random packing and structured packing；The material of the filler is ceramics, stainless steel, Al2O3, the Al that is modified of activated carbon, NACF, Fe or Pt2O3, Fe or One or more in the NACF that the activated carbon or Fe or Pt that Pt is modified are modified；The catalyst is the Al that activated carbon, NACF, Fe or Pt are modified2O3, Fe or the Pt activated carbon or Fe or Pt that are modified One or more in modified NACF.
- 10. the recycling method of nitrogen oxides according to claim 1, it is characterised in that：Liquid to after removal methanol Aqueous solution of nitric acid is added in phase.
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Cited By (1)
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| CN112759518A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Treatment method and system for byproduct nitric acid in process of preparing ethylene glycol from synthesis gas |
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