CN106117120B - A kind of technique and device of rectifying-Steam soak coupled method recycling pyridine - Google Patents
A kind of technique and device of rectifying-Steam soak coupled method recycling pyridine Download PDFInfo
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- CN106117120B CN106117120B CN201610722685.XA CN201610722685A CN106117120B CN 106117120 B CN106117120 B CN 106117120B CN 201610722685 A CN201610722685 A CN 201610722685A CN 106117120 B CN106117120 B CN 106117120B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
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Abstract
The present invention relates to techniques and device that a kind of rectifying Steam soak coupled method recycles pyridine, are as follows：Aqueous pyridine is entered into rectifying column, bottom of tower obtains anhydrous pyridine or other heavy constituents, and tower top obtains the azeotropic mixture of pyridine and water.An azeotropic mixture part flows back, and enters vapor permeable membrane dewatering system after part overheat, anhydrous pyridine is obtained after film multi-stage separation.Film separation system per-meate side is connected with vacuum system, prime penetrating fluid direct emission, and penetrating fluid of the rear class containing pyridine enters front rectifying column and be recycled.Present invention process process is simple, and low energy consumption, and no third component is added, and the rate of recovery is high.
Description
Technical field
The present invention relates to a kind of technique of pyridine recycling and devices more particularly to a kind of rectifying-vapor permeable membrane coupled method
The technique and device of pyridine are recycled, vapor permeable membrane application field is belonged to.
Background technology
Pyridine is important pesticide, medical material, and is good organic solvent and organic catalyst compound.Pyridine waste water
If direct emission, not only environment is caused to seriously endanger, but also great economic loss can be caused.Pyridine can be formed most with water
Low azeotropic mixture can not be detached using common rectificating method.Pyridine is dissolved in water, ethyl alcohol, ether equal solvent, and pyridine contains with water formation
Water 43%（Mass percent）Azeotropic mixture.Will produce pyridine, aqueous mixtures raffinate sometimes in the industrial production, at the same also for
The requirement of environmental protection needs to recycle the pyridine in pyridine aqueous mixtures.
Tradition separation pyridine aqueous mixtures are used using benzene as the method for the azeotropic distillation of entrainer, i.e., tower top obtains benzene water azeotropic
Object, bottom of tower obtain pyridine.It, can be to the pyridine row distillation again of bottom of tower in order to further increase the purity of pyridine.Benzene in benzene water azeotropic mixture
Content is both needed to steam from tower top up to 91.17% (mass percent), a large amount of benzene, and it is larger that there are energy consumptions, and operation is stringent, and benzene may
The shortcomings of pollution being brought to pyridine.Salt easily blocks and etching apparatus, and saline extraction is in actual industrial using few.Transformation essence
It evaporates flow by 2 different rectifying columns of operating pressure to be coupled, so that azeotropic composition is changed by changing pressure, thus across
More former azeotropic composition realizes separation, which can be to avoid the use of entrainer, but energy consumption is also bigger than normal.
Invention content
It is an object of the invention to propose a kind of method that rectifying-vapor permeable membrane coupled method carries out pyridine dehydration.Steam
Infiltration membrane technology, which is utilized, to be dissolved in film (absorption) property different from diffusion rate by each component in separating mixture and reaches point
From purpose, separation process do not limited by component vapor-liquid equilibrium, and the tradition such as distillation, extraction, absorption can be realized with low energy consumption
Method be difficult to the separation task completed, substituting traditional pyridine dehydration technique has prodigious advantage.This method has technique mistake
The characteristics of journey is simple, and safety coefficient is high, and the rate of recovery is high, and low energy consumption, cleanliness without any pollution.
A kind of technique of rectifying-vapor permeation recycling pyridine, includes the following steps：
Aqueous pyridine is carried out preliminary purification by the 1st step by way of rectifying, and tower top obtains the azeotropic mixture of pyridine and water,
Bottom of tower obtains pyridine and other heavy constituents；
An azeotropic mixture part for 2nd step, pyridine and water flows back, and enters vapor permeable membrane dewatering system after another part overheat
It is dehydrated, is recycled pyridine in vapor permeable membrane retention side, water is obtained in per-meate side.
In 2nd step, the steam of per-meate side passes through condensed in two stages in vapor permeable membrane dehydration；The first order is oozed
The penetrating fluid of transparent liquid direct emission, the second level is back to rectifying column recovery processing.
In 1st step, the operating pressure of rectifying column is 0~0.5Mpa.Feed liquid can be made to enter steam in vapour form in this way
Membrane separator group is permeated, mass transfer force is improved, saves energy consumption.
In 2nd step, by the way that the azeotropic mixture of pyridine and water is warming up to 90~150 DEG C after overheat.Can make in this way feed liquid with
Vapor form enters Steam soak membrane separator group, improves mass transfer force, and can reduce the water content in product.
In 2nd step, the per-meate side of vapor permeable membrane keeps pressure in 100~8000Pa by vacuumizing.
In 2nd step, vapor permeable membrane is made of 1~100 UF membrane units connected in series, parallel connection or series-parallel connection.If film point
It is too small from area, then it cannot reach separation accuracy, if UF membrane area is excessive, the energy consumption of system can be caused excessively high, passed through
Different disposal requirement and production capacity may be implemented in adjustment series connection and number in parallel.
In 2nd step, the material of vapor permeable membrane is polyvinyl alcohol film, polyimides, chitosan or molecular screen membrane.
The aqueous pyridine refers to the acid waste water containing pyridine generated in pyrethrins production process, and wherein pyridine contains
Measure about 15~20%, pH about 4.2~5.3；It is needed before carrying out rectifying plus alkali adjusts pH to neutrality.
A kind of rectifying-vapor permeation recycles the device of pyridine, includes：The tower top of rectifying column, rectifying column is provided with tower
Push up segregator, bottom of tower is provided with reboiler, the liquid-phase outlet of dephlegmator of top of the tower by superheater again with Steam soak membrane separator
The retention side entrance connection of group, the retention side outlet of Steam soak membrane separator group are connect with condenser, Steam soak UF membrane
The per-meate side of unit is connected with penetrating fluid condenser and vacuum pump.
The penetrating fluid condenser is by sequentially connected level-one penetrating fluid condenser and two level penetrating fluid condenser institute
Composition, two level penetrating fluid condenser are connect with rectifying column.
The Steam soak membrane separator group is to be serially connected by 1~100 Steam soak membrane separator, is in parallel or mixed
Connection is constituted.
Steam soak membrane material in Steam soak membrane separator is polyvinyl alcohol film, polyimides, chitosan or divides
Sub- sieve membrane.
Further include being useful for adjusting the pH value of aqueous pyridine to the pH adjustment portions of neutrality in the device.
Advantageous effect
Pyridine recycling can be effectively performed in pyridine recovery method provided by the invention, its moisture is made to be reduced to
0.01%（w/w）Below.Simultaneously, it is ensured that the infiltration water containing pyridine that Steam soak membrane separator group generates can be into one
Step recycles, and is lost almost without pyridine in technical process, and the content of organics in the waste water of direct emission is very low.
Description of the drawings
Fig. 1 is the flow diagram of pyridine retracting device provided by the invention.
1, rectifying column；2, dephlegmator of top of the tower；3, reboiler；4, superheater；5, Steam soak membrane separator group；6, it condenses
Device；7, level-one penetrating fluid condenser；8, two level penetrating fluid condenser；9, vacuum pump.
Specific implementation mode
Below by specific implementation mode, invention is further described in detail.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Specific skill is not specified in embodiment
Art or condition person carry out according to technology or condition described in document in the art or according to product description.Examination used
Production firm person is not specified in agent or instrument, and being can be with conventional products that are commercially available.
The value expressed using range format should be interpreted as not only in a flexible way including clearly enumerating as range
The numerical value of limit value, but also include all single numbers or the subinterval covered in the range, like each numerical value and sub-district
Between be expressly recited out.For example, the concentration range of " about 0.1% to about 5% " should be understood as including not only clearly enumerating
The concentration of about 0.1% to about 5% further includes the single concentration in how（Such as, 1%, 2%, 3% and 4%）The subinterval and（Example
Such as, 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%）.Heretofore described percentage in the case of no special instruction,
It refer to weight percent.
" one embodiment " for addressing in the present specification, " another embodiment ", " embodiment " etc., refer to
In conjunction with the specific features of embodiment description, structure or it is included at least one embodiment generally described herein.
It is not centainly to refer to the same embodiment that statement of the same race, which occur, in multiple places in the description.Furthermore, it is understood that in conjunction with any
When embodiment describes a specific features, structure or feature, what is advocated is that this spy is realized in conjunction with other embodiment
Sign, structure or feature are also fallen in the application scope of the claimed.
What is handled in following embodiment is the acid waste water containing pyridine generated in pyrethrins production process, wherein pyridine
Content about 15~20%, pH about 4.2~5.3.
The present invention detaches aqueous pyridine solution using rectifying-Steam soak membrane separation process, and film retains side tower reactor
The low-down pyridine product of water content can be obtained, the direct gas phase of tower top material of rectifying column enters Steam soak membranous system, simultaneously
Rear class penetrating fluid with pyridine enters rectifying column and further recycles.Entire process energy consumption is low, simple for process, realizes pyridine
The maximum rate of recovery and zero-emission.
Embodiment 1
1000kg/h pyridine waste water containing pyridine 20% is sent into rectifying column, rectifying column operating pressure is 0.1MPa, reflux ratio
It is 0.5.Tower top obtains the pyridine of water content about 42.5%, is superheated to 120 DEG C and enters by 6 vapor permeable membrane (every grade of membrane modules
Area is 30m2) infiltration membrane separator group 5 in series.Membranous system osmotic lateral pressure is controlled in 1000Pa.Water in feed liquid
It is condensed through level-one penetrating fluid condenser 7 and two level penetrating fluid condenser 8 through vapor permeable membrane, level-one penetrating fluid direct emission,
Two level penetrating fluid is directly entered the circulation and stress that rectifying column 1 carries out pyridine.
Embodiment 2
1000kg/h pyridine waste water containing pyridine 20% is sent into rectifying column, rectifying column operating pressure is 0.15MPa, reflux
Than being 0.9.Tower top obtains the pyridine of water content about 42.1%, is superheated to 140 DEG C and enters by 4 NaA molecular sieve vapor permeable membranes
(every grade of membrane module area is 10m2) infiltration membrane separator group 5 in series.Membranous system osmotic lateral pressure is controlled in 700Pa.
Water in feed liquid is condensed through vapor permeable membrane through level-one penetrating fluid condenser 7 and two level penetrating fluid condenser 8, level-one penetrating fluid
Direct emission, two level penetrating fluid are directly entered the circulation and stress that rectifying column 1 carries out pyridine.
Embodiment 3
1000kg/h pyridine waste water containing pyridine 20% is sent into rectifying column, rectifying column operating pressure is 0.20MPa.Tower top
The pyridine of water content about 41.8% is obtained, 130 DEG C is superheated to and enters by 10 NaA molecular sieve vapor permeable membrane (every grade of membrane modules
Area is 7m2) infiltration membrane separator group 5 in series.Membranous system osmotic lateral pressure is controlled in 2000Pa.Water in feed liquid is saturating
It crosses vapor permeable membrane to condense through level-one penetrating fluid condenser 7 and two level penetrating fluid condenser 8, level-one penetrating fluid direct emission, two
Grade penetrating fluid is directly entered the circulation and stress that rectifying column 1 carries out pyridine.
Embodiment 4
Rectifying column, rectifying column operation are sent into after adding alkali to adjust pH to neutrality the 1000kg/h pyridine waste water containing pyridine 20%
Pressure is 0.15MPa, reflux ratio 0.9.Tower top obtains the pyridine of water content about 42.1%, is superheated to 140 DEG C and enters by 4
(every grade of membrane module area is 10m to NaA molecular sieve vapor permeable membrane2) infiltration membrane separator group 5 in series.Membranous system permeates
Lateral pressure is controlled in 700Pa.Water in feed liquid permeates liquid condensing through vapor permeable membrane through level-one penetrating fluid condenser 7 and two level
Device 8 condenses, level-one penetrating fluid direct emission, and two level penetrating fluid is directly entered the circulation and stress that rectifying column 1 carries out pyridine.
Claims (1)
1. a kind of technique of rectifying-vapor permeation recycling pyridine, which is characterized in that include the following steps：1st step, will be aqueous
Pyridine carries out preliminary purification by way of rectifying, and tower top obtains the azeotropic mixture of pyridine and water, and bottom of tower obtains pyridine and other heavy
Component；The azeotropic mixture part of 2nd step, pyridine and water flows back, enter after another part overheat vapor permeable membrane dewatering system into
Row dehydration is recycled pyridine in vapor permeable membrane retention side, water is obtained in per-meate side；
In 2nd step, the steam of per-meate side passes through condensed in two stages in vapor permeable membrane dehydration；The penetrating fluid of the first order
The penetrating fluid of direct emission, the second level is back to rectifying column recovery processing；
In 1st step, the operating pressure of rectifying column is 0~0.5Mpa；In 2nd step, by after overheat by the azeotropic mixture of pyridine and water
It is warming up to 90~150 DEG C；In 2nd step, the per-meate side of vapor permeable membrane keeps pressure in 100~8000Pa by vacuumizing；
In 2nd step, vapor permeable membrane is made of 1~100 UF membrane units connected in series, parallel connection or series-parallel connection；
In 2nd step, the material of vapor permeable membrane is polyvinyl alcohol film, polyimides, chitosan or molecular screen membrane；
The aqueous pyridine refers to the acid waste water containing pyridine generated in pyrethrins production process, wherein pyridine content 15
~20%, pH 4.2~5.3；It is needed before carrying out rectifying plus alkali adjusts pH to neutrality.
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| CN107185265A (en) * | 2017-06-21 | 2017-09-22 | 武汉智宏思博化工科技有限公司 | The dehydration of organic solvent equipment that a kind of rectifying column is coupled with seepage slope membranous system |
| CN112121453B (en) * | 2020-09-10 | 2023-12-05 | 天津大学 | In-tower reactive distillation and membrane coupling process method and device for producing ethyl levulinate |
| CN114212941A (en) * | 2021-12-21 | 2022-03-22 | 江苏三吉利化工股份有限公司 | System and method for recovering MOE (metal oxide organic ether) in ethylene glycol monomethyl ether wastewater |
| CN116332836B (en) * | 2022-07-28 | 2024-03-26 | 四川熔增环保科技有限公司 | Method for recovering pyridine waste solvent |
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| CN101402568B (en) * | 2008-11-18 | 2011-08-10 | 南京工业大学 | Method for producing ethyl acetate with coupled reaction distillation and permeation steam generation |
| CN102887815B (en) * | 2012-07-25 | 2014-09-17 | 江苏九天高科技股份有限公司 | N-propanol refining technology |
| CN103071307B (en) * | 2013-01-23 | 2015-04-22 | 江苏九天高科技股份有限公司 | Rectification-steam penetration-coupled organic solvent dewatering method and device |
| CN103224456B (en) * | 2013-04-08 | 2015-04-22 | 江苏九天高科技股份有限公司 | Process and device for refining acetonitrile with a pervaporation method |
| CN103408514B (en) * | 2013-08-20 | 2015-06-17 | 江苏九天高科技股份有限公司 | Technique and device for recovering tetrahydrofuran by pervaporation method |
| CN103709022B (en) * | 2013-12-21 | 2015-09-02 | 江苏九天高科技股份有限公司 | A kind of pervaporation method reclaims technique and the device of butanone |
| CN104027996A (en) * | 2013-12-27 | 2014-09-10 | 江苏九天高科技股份有限公司 | A pervaporation rectification coupled system and a use thereof |
| CN103910605B (en) * | 2013-12-27 | 2016-04-27 | 江苏九天高科技股份有限公司 | The technique of a kind of infiltration evaporation system and refined biological propyl carbinol thereof |
| CN104130105B (en) * | 2014-06-25 | 2016-04-27 | 江苏九天高科技股份有限公司 | The method that in D-4-methylsulfonylphserine serine ethyl ester production, ethanol is recycled |
| CN104926690B (en) * | 2015-06-11 | 2017-07-14 | 江苏九天高科技股份有限公司 | The recovery process for purification and device of acetonitrile in a kind of synthesis for Ceftriaxone Sodium |
| CN105218317B (en) * | 2015-11-03 | 2017-08-25 | 江苏九天高科技股份有限公司 | The method and device that ethanol is reclaimed in a kind of hexanitrobibenzyl production |
| CN105778982A (en) * | 2016-04-29 | 2016-07-20 | 广西大学 | Method for simulating pyridine in gasoline through pervaporation membrane separation |
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