CN107540509A - A kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene - Google Patents
A kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene Download PDFInfo
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- CN107540509A CN107540509A CN201710847802.XA CN201710847802A CN107540509A CN 107540509 A CN107540509 A CN 107540509A CN 201710847802 A CN201710847802 A CN 201710847802A CN 107540509 A CN107540509 A CN 107540509A
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- butadiene
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Abstract
The present invention relates to a kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene, the crude butadiene from oxidative dehydrogenation butadiene product equipment enters preceding weight-removing column, tower reactor excision heavy constituent discharge, and tower top material enters extraction unit, obtains product butadiene.Compared with prior art, the de- density current journey that the present invention passes through weight-removing column before increase, remove the heavy constituent in crude butadiene charging, it is remarkably improved the stability and product qualification rate of the operation of oxidative dehydrogenation Butadiene Extraction Process extraction unit, greatly reduce the fluctuation of product butadiene purity, reduce the freshening of defective work, ensure the production of device continuous-stable, while also reduce the energy consumption of device.
Description
Technical field
The present invention relates to chemical products separation technology field, and the production of oxidative dehydrogenation process butadiene is reduced more particularly, to one kind
The method of alkynes content in product.
Background technology
Butadiene is important basic petrochemical raw material, is mainly used to produce butadiene rubber, butadiene-styrene rubber, nitrile rubber
And ABS resin etc., while be also a kind of important coating and Organic Chemicals.The production method of butadiene has C-4-fraction point
From with two kinds of synthetic method (including butane dehydrogenation, butylene dehydrogenation, butylene oxidation-dehydrogenation etc.).By cracker raw material lighting shadow
Ring, extraction process increases butadiene newly and is difficult to meet demand.Butylene oxidation-dehydrogenation is increasingly becoming fourth with higher conversion ratio and selectivity
One of main production line of diene.
Oxidative dehydrogenation Butadiene Extraction Process before China (1980) eighties, due to only being required to four total alkynes of carbon, extracting
Just without two extraction technological processes, as downstream unit is to alkynes, the understanding particularly to vinylacetylene and requirement, taking out part
Bill of lading member adds two extraction separating technologies.But because oxidative dehydrogenation thing needs the oil of carbon six to absorb, cause meeting in crude butadiene
With a small amount of component of carbon six.According to carbon four and the vapor liquid equilibrium of the oil of carbon six, still have a small amount of oil of carbon six and enter with carbon four
Extraction system, it is accumulated in extractant in running, and is dissolved each other with extractant, it is difficult to is removed, the separation to two extractions cause shadow
Ring, make the product butadiene medium vinyl acetylene content of two extraction tower tops exceeded.According to the operation of same device, to the second extraction tower
The fluctuation of vinylacetylene is pushed up, does not find the reason for real, does not more recognize it is the pollution for absorbing oil accumulation to solvent
Caused by influence；There is the exceeded situation of alkynes, general operation is to increase the load of the second extraction tower, increase solvent, increase
Reflux ratio；The extraction system repeatedly circulation of one extraction two, purification, to reach the purity requirement of product, this invisible fortune for adding device
Row cost.Another processing method is that the removing alkynes of the task is completed by the butadiene weight-removing column in extraction unit.Increase fourth
The load of diene weight-removing column, increases reflux ratio, and the regulation of reflux ratio is even bigger than former design load 2~2.5 times；Add device
Operation energy consumption, and butadiene weight-removing column is last knockout tower of whole flow process, easily causes the unqualified of tank field product, this is big
The big quality control risk for adding product；And follow-up operation load is high, operation risk is big, to the stabilization and continuous production of device
Impact.
The content of the invention
Extraction unit two extracts the problem of tower top alkynes content overproof, mainly vinylacetylene content overproof, according to country
Standard GB/T13291, the requirement of product butadiene medium vinyl acetylene content are less than 5PPM, in set oxidative dehydrogenation butadiene dress more
In putting, due to the pollution of extractant, the vinylacetylene on two extraction tops is often exceeded in practical operation, and device adjustment difficulty is big, increases
Add circulation time, cause operating cost high, the purpose of the present invention is exactly to be carried the defects of overcoming above-mentioned prior art to exist
For a kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene, is filled from oxidative dehydrogenation butadiene
The crude butadiene put enters preceding weight-removing column, tower reactor excision heavy constituent discharge, and tower top material enters extraction unit, obtains butadiene production
Product.
Preferably, the heavy constituent of preceding weight-removing column excision includes light dydrocarbon and light dydrocarbon above component, predominantly seven groups of carbon six and carbon
Point.The effect that heavy constituent is removed by preceding weight-removing column is to avoid these heavy constituents from being accumulated in extractant, pollutes extractant, causes
Second abstraction distillation system fluctuation of service causes alkynes content overproof in product butadiene.
It is furthermore preferred that described heavy constituent mainly includes the components such as pentane, amylene, hexane, hexene, heptane and heptene.
Preferably, the operating pressure of preceding weight-removing column is 0.3~0.6MPaG, and operation temperature is 40~60 DEG C.
Preferably, be additionally provided with knockout drum between preceding weight-removing column and extraction unit, the tower top discharging of preceding weight-removing column first produce into
Enter knockout drum, extraction unit is entered back into after evaporation.
Preferably, the overhead condensation mode of preceding weight-removing column is partial reflux or not flowed back,
When the mass content of carbon six is less than the second extraction tower side in 1000ppm or extraction unit in the heavy constituent of crude butadiene
When adopting light dydrocarbon and above mass content less than 5%, tower top does not flow back, and all extraction enters subsequent extraction unit to its top gaseous phase；
When the second extraction that the mass content of carbon six is more than or equal in 1000ppm or extraction unit in the heavy constituent of crude butadiene
When taking tower side to adopt light dydrocarbon and above mass content to be more than or equal to 5%, tower top partial reflux, increase partial reflux, increase in tower
Liquid phase mass transfer, heat transfer, further deviate from heavy constituent.
Preferably, the butadiene mass content in crude butadiene is more than 50%.
The thermal source of each device of the present invention preferentially utilizes circulation solvent heat or steam condensate heat in process system.
Compared with prior art, the present invention finds the second extraction tower top vinyl by the research to more set running gears
Acetylene content is exceeded, the reason for influenceing product butadiene quality, and passes through substantial amounts of contrast experiment and analyze data, it was confirmed that carbon
The accumulation of the heavy constituents such as six is main cause, therefore, by the optimization to flow, is increased before oxidative dehydrogenation process extraction unit
De- technological process again, removes heavy constituent, and the alkynes for effectively solving existing running gear influences asking for product butadiene fluctuation
Topic, and flow is simple, operation is low with investment cost, so as to improve the benefit of butadiene product equipment operation.
Brief description of the drawings
Fig. 1 is a kind of process chart of the present invention；
Fig. 2 is another process chart of the present invention；
Fig. 3 is the process chart of existing Butadiene Extraction unit；
In figure, T-1 is preceding weight-removing column, and T-2 is the first extraction tower, and T-3 is the second extraction tower, and T-4 is butadiene lightness-removing column,
T-5 is butadiene weight-removing column, and T-6 is alkynes flash column, and V-1 is knockout drum, and V-2 is charging evaporator.
Embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
A kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene, is filled from oxidative dehydrogenation butadiene
The crude butadiene put enters preceding weight-removing column, tower reactor excision heavy constituent discharge, and tower top material enters extraction unit, obtains butadiene production
Product.
As a kind of preferred embodiment of the present invention, the heavy constituent of preceding weight-removing column excision is included more than light dydrocarbon and light dydrocarbon
Component, predominantly carbon six and the component of carbon seven.It is furthermore preferred that described heavy constituent mainly includes pentane, amylene, hexane, hexene, heptan
The component such as alkane and heptene.
As a kind of preferred embodiment of the present invention, the operating pressure of preceding weight-removing column is 0.3~0.6MPaG, operation
Temperature is 40~60 DEG C.
As a kind of preferred embodiment of the present invention, knockout drum is additionally provided between preceding weight-removing column and extraction unit, it is preceding
First extraction enters knockout drum for the tower top discharging of weight-removing column, and extraction unit is entered back into after evaporation.
As a kind of preferred embodiment of the present invention, the overhead condensation mode of preceding weight-removing column for partial reflux or is not returned
Stream,
When the mass content of carbon six is less than the second extraction tower side in 1000ppm or extraction unit in the heavy constituent of crude butadiene
When adopting light dydrocarbon and above mass content less than 5%, tower top does not flow back, and all extraction enters subsequent extraction unit to its top gaseous phase；
When the second extraction that the mass content of carbon six is more than or equal in 1000ppm or extraction unit in the heavy constituent of crude butadiene
When taking tower side to adopt light dydrocarbon and above mass content to be more than or equal to 5%, tower top partial reflux, increase partial reflux, increase in tower
Liquid phase mass transfer, heat transfer, further deviate from heavy constituent.
As a kind of preferred embodiment of the present invention, crude butadiene is the components such as butylene, butane, butadiene, wherein
Butadiene content is more than 50%.
Embodiment 1
Crude butadiene from upstream enters preceding weight-removing column T1, weight-removing column before control as the S1 of feed carbon four from middle and upper part
T1 operating pressure is 0.5MPaG, and operation temperature is 53 DEG C, and tower top is according to the content of heavy constituent, using partial condensation reflux
Expect that S4, overhead extraction gas phase S3 enter the first extraction tower T2, then enter back into follow-up second extraction tower processing, tower reactor utilizes solvent
Waste heat or steam condensate heating, bottom heavy constituent is according to accumulation, row outside gap, as shown in Figure 1.
Entering in the first extraction tower after the entrance that table 1 below is taken off handle again after for certain device through above-mentioned flow in extraction unit
Material composition.
Table 1
| Extraction unit is fed | Form (wt%) |
| Carbon three | 0.0860 |
| Iso-butane | 0.5233 |
| Isobutene | 0.0389 |
| 1,3- butadiene | 70.9253 |
| Normal butane | 2.4187 |
| Butene-1 | 0.3584 |
| Trans-2-butene | 14.5329 |
| Cis-2-butene | 10.8041 |
| Vinylacetylene | 0.2535 |
| Light dydrocarbon and more than | 0.0590 |
Comparative example 1
Crude butadiene from upstream is sent into charging evaporator V-2, the material after evaporation is directly sent as the S1 of feed carbon four
Enter the first extraction tower T2 start to process in subsequent extraction unit, as shown in figure 3, extraction unit includes the first extraction being sequentially connected
Take tower T-2, the second extraction tower T-3, butadiene lightness-removing column T-4, butadiene weight-removing column T-5 and alkynes flash column T-6.
The result of com-parison and analysis embodiment 1 and comparative example 1, it is as shown in table 2 below.
Table 2 second extracts tower top vinylacetylene (VA) comparision contents
| Before increase weight-removing column (i.e. comparative example 1) | After increase weight-removing column (i.e. embodiment 1) | |
| VA(ppm) | 0~50 | ≤5 |
| Vibration frequency (times/day) | 15~30 | It is stable |
By that can be obtained in upper table, for the S1 of feed carbon four of same oxidative dehydrogenation butadiene product equipment discharge, weight is taken off before increase
Tower significantly reduces the content and fluctuation number of the second extraction tower top ethylene vinyl；On the one hand the steady of plant running is added
It is fixed, the operating load of aftertreatment device is on the other hand reduced, greatly reduces operating cost, for the fortune of butadiene product equipment
Row is stable to have significantly effect with energy-saving.
Embodiment 2
Compared with the technological process of embodiment 1, except between preceding weight-removing column T1 and the first extraction tower T1 of extraction unit
Be additionally provided with outside knockout drum V1, remaining, idiographic flow is as shown in Figure 2.
Embodiment 3
Compared with Example 1, the overwhelming majority is all identical, except in the present embodiment：
Preceding weight-removing column T1 operating pressure 0.3MPaG, operation temperature are 40 DEG C.
Embodiment 4
Compared with Example 1, the overwhelming majority is all identical, except in the present embodiment：
Preceding weight-removing column T1 operating pressure 0.4MPaG, operation temperature are 45 DEG C.
Embodiment 5
Compared with Example 1, the overwhelming majority is all identical, except in the present embodiment：
Preceding weight-removing column T1 operating pressure 0.6MPaG, operation temperature are 60 DEG C.
The invention provides a kind of Oxidative Dehydrogenation of Butene into Butadiene refining spearation technique, has significant economic benefit.
Illustrated in conjunction with the embodiments, the personnel of association area can suitably be changed according to method provided by the invention completely
Or change with combining, to realize the technology.It is it should be strongly noted that all these by technological process provided by the invention
Similar change or change are carried out with reconfiguring, it is apparent to those skilled in the art, it is considered as
In the spirit of the present invention, scope and content.
Claims (7)
- A kind of 1. method for reducing alkynes content in oxidative dehydrogenation process product butadiene, it is characterised in that from oxidative dehydrogenation The crude butadiene of butadiene product equipment processed enters preceding weight-removing column, tower reactor excision heavy constituent discharge, and tower top material enters extraction unit, obtained To product butadiene.
- 2. a kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene according to claim 1, it is special Sign is that the heavy constituent of preceding weight-removing column excision includes light dydrocarbon and light dydrocarbon above component.
- 3. a kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene according to claim 2, it is special Sign is that described heavy constituent includes pentane, amylene, hexane, hexene, heptane and heptene.
- 4. a kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene according to claim 1, it is special Sign is that the operating pressure of preceding weight-removing column is 0.3~0.6MPaG, and operation temperature is 40~60 DEG C.
- 5. a kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene according to claim 1, it is special Sign is, knockout drum is additionally provided between preceding weight-removing column and extraction unit, and first extraction enters knockout drum for the tower top discharging of preceding weight-removing column, Extraction unit is entered back into after evaporation.
- 6. a kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene according to claim 1, it is special Sign is that the overhead condensation mode of preceding weight-removing column for partial reflux or does not flow back,When the mass content of carbon six is adopted less than the second extraction tower side in 1000ppm, or extraction unit in the heavy constituent of crude butadiene When light dydrocarbon and above mass content are less than 5%, tower top does not flow back, and all extraction enters subsequent extraction unit to its top gaseous phase；When the second extraction tower that the mass content of carbon six is more than or equal in 1000ppm or extraction unit in the heavy constituent of crude butadiene When light dydrocarbon and above mass content are adopted more than or equal to 5% in side, tower top partial reflux.
- 7. a kind of method for reducing alkynes content in oxidative dehydrogenation process product butadiene according to claim 1, it is special Sign is that the butadiene mass content in crude butadiene is more than 50%.
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| CN201710847802.XA CN107540509B (en) | 2017-09-19 | 2017-09-19 | Method for reducing alkyne content in butadiene product in oxidative dehydrogenation process |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113499598A (en) * | 2021-08-02 | 2021-10-15 | 山东鸿瑞新材料科技有限公司 | Device for recovering, separating and utilizing tail gas of medium-molecular polyisobutylene |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105246864A (en) * | 2013-03-28 | 2016-01-13 | 环球油品公司 | Process for the purification of 1,3-butadiene from an oxidative dehydrogenation process |
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- 2017-09-19 CN CN201710847802.XA patent/CN107540509B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105246864A (en) * | 2013-03-28 | 2016-01-13 | 环球油品公司 | Process for the purification of 1,3-butadiene from an oxidative dehydrogenation process |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113499598A (en) * | 2021-08-02 | 2021-10-15 | 山东鸿瑞新材料科技有限公司 | Device for recovering, separating and utilizing tail gas of medium-molecular polyisobutylene |
| CN113499598B (en) * | 2021-08-02 | 2022-05-27 | 山东鸿瑞新材料科技有限公司 | Device for recovering, separating and utilizing tail gas of medium-molecular polyisobutylene |
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Address after: 201210 Zhongke Road 699, China (Shanghai) Free Trade Pilot Area, Shanghai Applicant after: Wison Engineering (China) Ltd. Address before: 201203 No. 1399 Zhangheng Road, Zhangjiang High-tech Park, Pudong New Area, Shanghai Applicant before: Wison Engineering (China) Ltd. |
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