CN107935807A - A kind of system and method for recycling refined methyl cyclopentane and application thereof - Google Patents
A kind of system and method for recycling refined methyl cyclopentane and application thereof Download PDFInfo
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- CN107935807A CN107935807A CN201711235438.8A CN201711235438A CN107935807A CN 107935807 A CN107935807 A CN 107935807A CN 201711235438 A CN201711235438 A CN 201711235438A CN 107935807 A CN107935807 A CN 107935807A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
- C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
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Abstract
The present invention relates to a kind of system and method for recycling refined methyl cyclopentane and application thereof, the system comprises sequentially connected de- light unit, purifier units and solvent recovery unit, further include heat exchange unit；It is the first extractive distillation column to take off light unit；Purifier units are the second extractive distillation column；Heat exchange unit includes each independent First Heat Exchanger, the second heat exchanger and the 3rd heat exchanger；Raw material intake line connects feed(raw material)inlet on the first extractive distillation column after passing through First Heat Exchanger；The bottom of towe of first extractive distillation column is equipped with the first pipeline, and so on.Combination of the extractant including any one in sulfolane, ethylene glycol, glycerine, NMF, NMP and DMF or at least two in the method, the mixed solvent formed with eutectic solvent compounding.The present invention can disposably purify out purity>The methyl cyclopentane product of 99.95wt%, the rate of recovery are more than 99%.
Description
Technical field
The present invention relates to the organic separation technology field of chemical industry, more particularly to a kind of system for recycling refined methyl cyclopentane and
Method and application thereof.
Background technology
Hydrocarbon is raffinated oil can produce hexamethylene, methyl cyclopentane, butane, pentane, benzene with industrial process such as Cyclohexanone Productions
Deng accessory substance, methyl cyclopentane therein may be used as solvent, chromatography standard substance, organic synthesis raw material etc., its is widely used,
It is expensive, if the methyl cyclopentane in accessory substance can be recycled, good economic benefit can be obtained.But at present
In the market low-purity methyl cyclopentane yield is high, price is general, high-purity methyl pentamethylene low output, expensive.Following
Chemical Engineering Technology developing direction is fine chemistry industry.The fine chemicals that production purity is high, added value is high is that the development of chemical industry becomes
Gesture.Therefore the method for purification of exploitation high-purity methyl pentamethylene is the only way of enterprise development and following chemical industry development.
Methyl cyclopentane is approached with n-hexane boiling point, and methyl cyclopentane and benzene, hexamethylene and benzene can also form azeotropic mixture, because
This is difficult to be separated with conventional rectification means.For the purification of methyl cyclopentane, substantial amounts of research has been carried out both at home and abroad, it is common
Method is azeotropic distillation or extracting rectifying.
Rectifying is to utilize distribution of the different components between vapor-liquid two phases, passes through the mass transfer between multiple gas-liquid two-phase and heat transfer
To reach separated purpose.For different separation objects, rectificating method also can difference.For example, separating alcohol and water
Binary system.Since second alcohol and water can form azeotropic mixture, and azeotropic temperature under normal pressure and the boiling temperature of ethanol are extremely
It is close, so can only obtain the mixture of second alcohol and water using conventional distillation method, and absolute ethyl alcohol can not be obtained.For this reason,
The third material is added in ethanol-water system, which is referred to as entrainer.Entrainer has energy and by one in piece-rate system
Kind or several materials form the characteristic of minimum azeotropic mixture.Entrainer will be steamed in the form of azeotropic mixture from tower top in distillation process
Go out, tower reactor then obtains absolute ethyl alcohol.This method is referred to as azeotropic distillation.For the purification of methyl cyclopentane, azeotropic essence
It is methanol to evaporate common entrainer, but flow is longer, equipment and place investment are big, energy consumption is larger, and purity only up to reach
99.9wt%.
Extracting rectifying is to be continuously added to higher boiling additive to rectifying tower top, is changed in feed liquid by opposite between separation component
Volatility, makes conventional distillation be difficult to separated liquid mixture and becomes prone to a kind of separated special extract rectification method.For methyl
The purification of pentamethylene, extracting rectifying often have repefral, 1-methyl-2-pyrrolidinone, patent with extractant
Repefral and 1-methyl-2-pyrrolidinone is respectively adopted as extraction in CN1765857A and patent CN103664446A
Agent, separates n-hexane and methyl cyclopentane, the methyl cyclopentane purity Fen of overhead extraction Bie Wei≤84wt% He≤90.8wt%,
The high-purity requirement of 99.95wt% is not reached much.Therefore, it is necessary to develop efficient methyl cyclopentane high-efficiency recycling device
And method.
The content of the invention
In view of problems of the prior art, it is an object of the present invention to provide a kind of methyl cyclopentane recycling essence
System and method processed, purify out purity>The methyl cyclopentane product of 99.95wt%, at the same it is as far as possible energy-saving.
For this purpose, the present invention adopts the following technical scheme that：
In a first aspect, the present invention provides a kind of system for recycling refined methyl cyclopentane, the system comprises be sequentially connected
De- light unit, purifier units and solvent recovery unit, further include heat exchange unit；
Wherein, the de- light unit is the first extractive distillation column；The purifier units are the second extractive distillation column；It is described to change
Hot cell includes each independent First Heat Exchanger, the second heat exchanger and the 3rd heat exchanger；
Raw material intake line connects feed(raw material)inlet on first extractive distillation column after passing through the First Heat Exchanger；Institute
The bottom of towe for stating the first extractive distillation column is equipped with the first pipeline, and first pipeline, which passes through, connects described the after second heat exchanger
Two extractive distillation columns；The bottom of towe of second extractive distillation column is equipped with the second pipeline, and second pipeline is changed through the described 3rd
The solvent recovery unit is connected after hot device.
Preferably, the solvent recovery unit is rectifying column.
Preferably, the double-level-metal screen waviness packings with diamond shape diversion window are filled with inside the rectifying column.
Preferably, the inside of first extractive distillation column is filled out filled with the double-level-metal screen waviness with diamond shape diversion window
Material.
Preferably, the inside of second extractive distillation column is filled out filled with the double-level-metal screen waviness with diamond shape diversion window
Material.Double-level-metal screen waviness packings with diamond shape diversion window have flux height, pressure drop is low, energy consumption is low, filling intensity is high, surface
The characteristics of wetting and spreading is good, gas-liquid mass transfer is efficient, while the increase of the woven wire number of plies, enhance the overall strong of filler
Degree, improves the service life of filler, can help to reduce tower height as tower resolution element, save the device space；And be conducive to carry
High separating efficiency.
Preferably, the First Heat Exchanger, second heat exchanger and the 3rd heat exchanger are each independently board-like
Heat exchanger.
Preferably, the extractant outlet of the solvent recovery unit is equipped with return pipeline, and the return pipeline sequentially passes through
First extractive distillation column is connected after 3rd heat exchanger, the second heat exchanger, First Heat Exchanger.
Second aspect, the present invention provide a kind of method for recycling refined methyl cyclopentane, and the method utilizes such as first party
System described in face carries out.
Preferably, include the following steps：
(1) after extractant and raw material containing methyl cyclopentane being carried out first time heating through First Heat Exchanger, introduce
First extractive distillation column carries out first time rectifying extraction, overhead extraction light component；
(2) step (1) remaining ingredient carries out second of heating from the bottom of towe of the first extractive distillation column through the second heat exchanger
Afterwards, into carrying out second of rectifying extraction, overhead extraction methyl cyclopentane in the second extractive distillation column；
(3) step (2) remaining ingredient carries out third time heating from the bottom of towe of the second extractive distillation column through the 3rd heat exchanger
Afterwards, into being separated in solvent recovery unit, heavy constituent and extractant are obtained.
Preferably, the extractant includes sulfolane, ethylene glycol, glycerine, N- N-formyl morpholine Ns (NMF), N- methylpyrroles
In alkanone (NMP) and dimethylformamide (DMF) any one or at least two combination, with eutectic solvent compounding form
Mixed solvent.Wherein, it is typical but non-limiting to be combined as：The group of the combination of sulfolane and ethylene glycol, glycerine and NMF
Close, the combination of NMP and DMF, the combination of NMF, NMP and DMF, the combination of sulfolane, ethylene glycol, glycerine and DMF.Sulfolane,
Ethylene glycol, glycerine, N- N-formyl morpholine Ns (NMF), 1-methyl-2-pyrrolidinone (NMP) and dimethylformamide (DMF) are conventional
Organic extractant, eutectic solvent, is a kind of green solvent, as a kind of special ionic liquid, has good dissolubility,
Inside has hydrogen bond and hydrogen bond network structure, and its molecular structure can design, function is adjustable, can be changed by intermolecular force
Become the relative volatility of thing system, break azeotropic etc., compared to conventional organic extractant after two parts compounding, its with low volatility,
The advantages that highly dissoluble, dosage are few, property is stable, hypotoxicity.
Preferably, the eutectic solvent includes hydrogen bond receptor and hydrogen bond donor.
Preferably, the hydrogen bond receptor includes tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, the tetrabutyl
Ammonium iodide, tetrabutyl fluorination phosphorus, tetrabutyl phosphorus chloride, tetrabutyl phosphonium bromide phosphorus, tetrabutyl iodate phosphorus, choline chloride, glycine betaine, chlorine
Change in benzyl triethyl ammonium ammonium and hydrogen sulfate tetrabutylammonium any one or at least two combination.Wherein, it is typical but unrestricted
Property is combined as：The combination of tetrabutyl ammonium fluoride and tetrabutyl phosphorus chloride, the combination of tetrabutyl iodate phosphorus and choline chloride, chlorination
Benzyl triethyl ammonium ammonium and the combination of hydrogen sulfate tetrabutylammonium, the combination of tetrabutylammonium chloride, tetrabutyl fluorination phosphorus and glycine betaine, four
The combination of butylammonium bromide, tetrabutylammonium iodide, tetrabutyl phosphonium bromide phosphorus, choline chloride and hydrogen sulfate tetrabutylammonium.
Preferably, the hydrogen bond donor includes formamide, acetamide, propionamide, ethylene glycol, propane diols, glycerine, isopropyl
Alcohol, hexylene glycol, sorbierite, butanediol, glycolic, malic acid, lactic acid, citric acid, maleic acid, aconitic acid, levulic acid, urine
Element, malonyl urea, thiocarbamide, lysine, tryptophan, phenylalanine, methionine, threonine, isoleucine, leucine, figured silk fabrics ammonia
Acid, alanine, glutamic acid, asparatate, glycine, cystine, proline, tyrosine, serine, glucose, fructose, wood
In sugar, sucrose and maltose any one or at least two combination.Wherein, it is typical but non-limiting to be combined as：Formyl
The combination of the combination of the combination of amine and butanediol, sorbierite and urea, malonyl urea and lysine, tryptophan, phenylalanine with
The combination of fructose, the combination of glycolic, valine, propionamide and maltose.
Preferably, the molar ratio of hydrogen bond receptor described in the eutectic solvent and the hydrogen bond donor is 1:(1~10),
Such as 1:1、1:2、1:3、1:4、1:5、1:6、1:7、1:8、1:9 or 1:10 etc..
Preferably, the eutectic solvent is stirred at 80 DEG C~100 DEG C by the hydrogen bond receptor with the hydrogen bond donor
To transparent and obtain, such as 80 DEG C, 81 DEG C, 82 DEG C, 83 DEG C, 85 DEG C, 88 DEG C, 90 DEG C, 91 DEG C, 92 DEG C, 95 DEG C, 98 DEG C, 99 DEG C
Or 100 DEG C etc..
Preferably, the proportion of eutectic solvent described in the extractant is 1~30wt%, such as 1wt%, 2wt%,
5wt%, 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt% or 30wt% etc..
Preferably, the mass ratio of the extractant and the raw material is (2~6):1, such as 2:1、2.2:1、2.5:1、
2.8:1、3:1、3.2:1、3.5:1、3.8:1、4:1、4.2:1、4.5:1、4.8:1、5:1、5.2:1、5.5:1、5.8:1 or 6:1
Deng.
Preferably, 1~2MPa of pressure of first extractive distillation column, for example, 1Mpa, 1.1Mpa, 1.2Mpa, 1.3Mpa,
1.4Mpa, 1.5Mpa, 1.6Mpa, 1.7Mpa, 1.8Mpa, 1.9MPa or 2MPa etc., column bottom temperature are 100~120 DEG C, such as
100 DEG C, 102 DEG C, 105 DEG C, 108 DEG C, 110 DEG C, 112 DEG C, 115 DEG C, 118 DEG C or 120 DEG C etc.；Tower top temperature is 20~30 DEG C,
Such as 20 DEG C, 21 DEG C, 22 DEG C, 23 DEG C, 24 DEG C, 25 DEG C, 26 DEG C, 27 DEG C, 28 DEG C, 29 DEG C or 30 DEG C etc..
Preferably, the pressure of second extractive distillation column is 1~2MPa, for example, 1Mpa, 1.1Mpa, 1.2Mpa,
1.3Mpa, 1.4Mpa, 1.5Mpa, 1.6Mpa, 1.7Mpa, 1.8Mpa, 1.9MPa or 2MPa etc., column bottom temperature are 120~160
DEG C, for example, 120 DEG C, 122 DEG C, 125 DEG C, 128 DEG C, 130 DEG C, 132 DEG C, 135 DEG C, 138 DEG C DEG C, 140 DEG C, 142 DEG C, 145 DEG C,
148 DEG C, 150 DEG C, 152 DEG C, 155 DEG C, 158 DEG C or 160 DEG C etc.；Tower top temperature be 70~90 DEG C, such as 70 DEG C, 72 DEG C, 75 DEG C,
78 DEG C, 80 DEG C, 82 DEG C, 85 DEG C, 88 DEG C or 90 DEG C etc..
Preferably, the pressure of rectifying column 3 is 1~2MPa, for example, 1Mpa, 1.1Mpa, 1.2Mpa, 1.3Mpa, 1.4Mpa,
1.5Mpa, 1.6Mpa, 1.7Mpa, 1.8Mpa, 1.9MPa or 2MPa etc., column bottom temperature be 200~240 DEG C, such as 200 DEG C, 202
℃、205℃、208℃、210℃、212℃、215℃、218℃、220℃、222℃、225℃、228℃、230℃、232℃、
235 DEG C, 238 DEG C or 240 DEG C etc.；Tower top temperature be 80~100 DEG C, such as 80 DEG C, 82 DEG C, 85 DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 95
DEG C, 98 DEG C or 100 DEG C etc..
Preferably, the reflux ratio of first extractive distillation column be 0.1~0.5, such as 0.1,0.12,0.15,0.18,
0.2nd, 0.22,0.25,0.28,0.3,0.32,0.35,0.38,0.4,0.42,0.45,0.48 or 0.5 etc., preferably 0.2~0.3.
Preferably, the reflux ratio of second extractive distillation column is 5~10, such as 5,5.5,6,6.5,6,6.5,7,7.5
Or 8 etc., preferably 7~8.
Preferably, the reflux ratio of rectifying column 3 be 1~2, such as 1,1.1,1.2,1.3,1.4,1.5,1.6,1.7,1.8,
1.9 or 2 etc., preferably 1.2~1.6.
Preferably, extractant obtained by step (4) returns to first extractive distillation column after being cooled down through heat exchange unit.
As currently preferred technical solution, the method for the refined methyl cyclopentane of recycling includes the following steps：
(1) it is (2~6) according to mass ratio by extractant and raw material containing methyl cyclopentane:1 through First Heat Exchanger into
After row heats up for the first time, introduce the first extractive distillation column and carry out first time rectifying extraction, 1~2MPa of tower pressure interior force, column bottom temperature
For 100~120 DEG C, tower top temperature is 20~30 DEG C, and reflux ratio is 0.1~0.5；Overhead extraction light component；Wherein, the extraction
Agent includes any one in sulfolane, ethylene glycol, glycerine, N- N-formyl morpholine Ns, 1-methyl-2-pyrrolidinone and dimethylformamide
Kind or at least two combination, the mixed solvent formed with accounting for the eutectic solvent compounding that extractant proportion is 1~30wt%；Institute
It is 1 to state eutectic solvent to include molar ratio:The hydrogen bond receptor and hydrogen bond donor of (1~10) are stirred to saturating at 80 DEG C~100 DEG C
Eutectic solvent obtained from bright；The hydrogen bond receptor include tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide,
Tetrabutylammonium iodide, tetrabutyl fluorination phosphorus, tetrabutyl phosphorus chloride, tetrabutyl phosphonium bromide phosphorus, tetrabutyl iodate phosphorus, choline chloride, sweet tea
In dish alkali, benzyltriethylammonium chloride and hydrogen sulfate tetrabutylammonium any one or at least two combination；The hydrogen bond supplies
Body include formamide, acetamide, propionamide, ethylene glycol, propane diols, glycerine, isopropanol, hexylene glycol, sorbierite, butanediol,
Glycolic, malic acid, lactic acid, citric acid, maleic acid, aconitic acid, levulic acid, urea, malonyl urea, thiocarbamide, lysine, color
Propylhomoserin, phenylalanine, methionine, threonine, isoleucine, leucine, valine, alanine, glutamic acid, asparagine
It is any one in acid, glycine, cystine, proline, tyrosine, serine, glucose, fructose, xylose, sucrose and maltose
Kind or at least two combination；
(2) step (1) remaining ingredient carries out second of heating from the bottom of towe of the first extractive distillation column through the second heat exchanger
Afterwards, into carrying out second of rectifying extraction in the second extractive distillation column, the pressure in tower is 1~2MPa, column bottom temperature for 120~
160 DEG C, tower top temperature is 70~90 DEG C, and reflux ratio is 5~10, overhead extraction methyl cyclopentane；
(3) step (2) remaining ingredient carries out third time heating from the bottom of towe of the second extractive distillation column through the 3rd heat exchanger
Afterwards, into being separated in rectifying column, the pressure in tower is 1~2MPa, and column bottom temperature is 200~240 DEG C, tower top temperature 80
~100 DEG C, reflux ratio is 1~2, obtains heavy constituent and extractant, and gained extractant is carried out after progressively cooling down through heat exchange unit
First extractive distillation column is returned, realizes the recycling of extractant and heat.
The third aspect, the present invention provides the purposes for the method that refined methyl cyclopentane is recycled as described in second aspect, described
Method is used for purification methyl ring penta in Aromatic raffinate, Cyclohexanone Production accessory substance fuel oil, cyclohexanol production accessory substance
Alkane.
Green, high selectivity, the extractant of highly dissoluble are developed, is to realize the pass that methyl cyclopentane high efficiente callback utilizes
Key.
Compared with prior art, the present invention at least has the advantages that：
1. system provided by the present invention can disposably purify out purity>The methyl cyclopentane product of 99.95wt%, recycling
Rate is more than 99%；
2. extractant effect of extracting is good, preparation is simple, solvent recovering rate is high, regeneration energy consumption is low；
3. technological process is simple, effectively energy-saving；
4. the extractant used in the present invention is given birth to available for the chemical industry such as Aromatic raffinate or Cyclohexanone Production accessory substance fuel oil
The purification of methyl cyclopentane during production, has universality.
Brief description of the drawings
Fig. 1 is the schematic diagram that methyl cyclopentane recycles refining system in the specific embodiment of the invention
The mark in the figure shows：1- extractive distillation columns I；2- extractive distillation columns II；3- rectifying columns；The first plate-type heat-exchanges of 4-
Device, the second plate heat exchangers of 5-, 6- three-plate types heat exchanger, 7- take off light unit, 8- purifier units, 9- solvent recovery units, 10-
Heat exchange unit
Embodiment
Further illustrate technical scheme below with reference to the accompanying drawings and specific embodiments.But following reality
Example is only the simple example of the present invention, does not represent or limit the scope of the present invention, protection scope of the present invention
It is subject to claims.
Embodiment 1
A kind of system for recycling refined methyl cyclopentane, as shown in Figure 1, taking off light unit 7, purification list including sequentially connected
Member 8 and solvent recovery unit 9, further include heat exchange unit 10；
Wherein, it is extractive distillation column I1 to take off light unit 7；Purifier units 8 are extractive distillation column II2；Heat exchange unit 10 includes
Each independent the first plate heat exchanger 4, the second plate heat exchanger 5 and three-plate type heat exchanger 6；The solvent recovery unit is
Rectifying column 3；Raw material intake line passes through the feed(raw material)inlet connected after the first plate heat exchanger 4 on extractive distillation column I1；Extraction essence
The bottom of towe for evaporating tower I1 is equipped with the first pipeline, through the second plate heat exchanger 5 after connect extractive distillation column II2；Extractive distillation column II2
Bottom of towe be equipped with the second pipeline, through three-plate type heat exchanger 6 after connect recovery unit 9；Rectifying column 3, extractive distillation column I1 extractions
Rectifying column II2 and inside is taken to be filled with the double-level-metal screen waviness packings with diamond shape diversion window.The extraction of solvent recovery unit 9
Take agent outlet to be equipped with return pipeline, sequentially pass through three-plate type heat exchanger 6, the second plate heat exchanger 5, the first plate heat exchanger 4
Extractive distillation column I1 is connected afterwards.
The fuel oil pair produced using above device from certain 100,000 tons/year of cyclohexanone production apparatus cyclohexane refining stage
Refined methyl cyclopentane is recycled in product, step is as follows：
1) it is 2 according to mass ratio by extractant and raw material:After 1 carries out first time heating through the first plate heat exchanger 4, draw
Enter extractive distillation column I1 and carry out first time rectifying extraction, 27 DEG C of tower pressure interior force 1.4MPa, tower top temperature, 108 DEG C of bottom temperature, is returned
Stream is than being 0.1；Overhead extraction light component；Wherein, the composition of extractant is：NMF contents are 41wt%；Eutectic solvent (DES)
Content is 2wt%；Sulfolane content is 57wt%.DES is 1 by molar ratio:1 hydrogen bond receptor and hydrogen bond donor stirs at 80 DEG C
Mix to eutectic solvent obtained from transparent；Hydrogen bond receptor is tetrabutylammonium bromide, and hydrogen bond donor is：Ethylene glycol；
2) step 1) remaining ingredient is carried out second from the bottom of towe of extractive distillation column I1 through the second heat exchanger 5 after heating up,
Carry out second of rectifying extraction into extractive distillation column II2, the pressure in tower is 1.4MPa, 82 DEG C of tower top temperature, tower reactor temperature
142 DEG C of degree, reflux ratio 5, overhead extraction methyl cyclopentane；
3) after step 2) remaining ingredient is from the bottom of towe of extractive distillation column II2 through the progress third time heating of the 3rd heat exchanger 6,
Separated into rectifying column 3, the pressure in tower is 1.45MPa, 95 DEG C of tower top temperature, 218 DEG C of bottom temperature, and reflux ratio is
2, heavy constituent and extractant are obtained, extractant returns to extractive distillation column I1 after progressively being cooled down through heat exchange unit 10, realizes
The recycling of extractant and heat.
The hexahydrotoluene product purity of extraction is 99.96wt% at the top of extractive distillation column II2, the rate of recovery 99.02%.
Embodiment 2
System is same as Example 1, and method is similar, unlike：
The composition of extractant is：DMF contents are 80wt%, and DES contents are 20wt%；DES is 1 by molar ratio:5 hydrogen bond
Acceptor and hydrogen bond donor are stirred at 90 DEG C to eutectic solvent obtained from transparent；Hydrogen bond receptor is：Choline chloride, hydrogen bond supply
Body is levulic acid.Extractive distillation column I1 operating pressures 1.4MPa, 27.5 DEG C of tower top temperature, 105 DEG C of bottom temperature, reflux ratio are
0.3；Extractive distillation column II2 operating pressures 1.4MPa, 81 DEG C of tower top temperature, 140 DEG C of bottom temperature, reflux ratio 8；Rectifying column 3
95 DEG C of operating pressure 1.5MPa, tower top temperature, 200 DEG C of bottom temperature, reflux ratio 1.5；
The hexahydrotoluene product purity of extraction is 99.97w% at the top of extractive distillation column II2, the rate of recovery 99.05%.
Embodiment 3
System is same as Example 1, and method is similar, unlike：
The composition of extractant is：Sulfolane content is 45wt%；DES contents 30wt%；Ethylene glycol content is 25wt%.
DES is 1 by molar ratio:10 hydrogen bond receptor and hydrogen bond donor is stirred at 100 DEG C to eutectic solvent obtained from transparent；Hydrogen
Key acceptor is：Glycine betaine, hydrogen bond donor are urea.Extractive distillation column I1 operating pressures 1.4MPa, 28 DEG C of tower top temperature, tower reactor temperature
Spend 110 DEG C of temperature, reflux ratio 0.5；Extractive distillation column II2 operating pressures 1.4MPa, 80 DEG C of tower top temperature, bottom temperature temperature
140 DEG C, reflux ratio 10；95 DEG C of rectifying column operating pressure 1.5MPa, tower top temperature, 210 DEG C of bottom temperature, reflux ratio 1.
The hexahydrotoluene product purity of extraction is 99.96wt% at the top of extractive distillation column II2, the rate of recovery 99.00%.
Comparative example 1
With differing only in for embodiment 1：Extractant replaces with repefral.
The hexahydrotoluene product purity of extraction is 76wt% at the top of extractive distillation column II2, the rate of recovery 81%.
Comparative example 2
With differing only in for embodiment 1：Extractant replaces with 1-methyl-2-pyrrolidinone.
The hexahydrotoluene product purity of extraction is 81wt% at the top of extractive distillation column II2, the rate of recovery 85%.
Comparative examples and comparative example 1~2 understand, sulfolan of the present invention, ethylene glycol, glycerine, NMF, NMP and DMF
For conventional organic extractant, its repefral and N- methylpyrroles compared with after eutectic solvent two parts compounding
The existing conventional organic extractant such as alkanone, obtains unexpected technique effect, gained hexahydrotoluene product purity be and
The rate of recovery all greatly improves, reach 99.95wt% high-purity requirement and the rate of recovery be more than 99%, achieve new breakthrough.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological process, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc., all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
- A kind of 1. system for recycling refined methyl cyclopentane, it is characterised in that the system comprises it is sequentially connected take off light unit, Purifier units and solvent recovery unit, further include heat exchange unit；Wherein, the de- light unit is the first extractive distillation column；The purifier units are the second extractive distillation column；The heat exchange is single Member includes each independent First Heat Exchanger, the second heat exchanger and the 3rd heat exchanger；Raw material intake line connects feed(raw material)inlet on first extractive distillation column after passing through the First Heat Exchanger；Described The bottom of towe of one extractive distillation column is equipped with the first pipeline, and first pipeline connects second extraction after passing through second heat exchanger Take rectifying column；The bottom of towe of second extractive distillation column is equipped with the second pipeline, and second pipeline passes through the 3rd heat exchanger After connect the solvent recovery unit.
- 2. the system of the refined methyl cyclopentane of recycling as claimed in claim 1, it is characterised in that the solvent recovery unit is Rectifying column；Preferably, the double-level-metal screen waviness packings with diamond shape diversion window are filled with inside the rectifying column.
- 3. the system of the refined methyl cyclopentane of recycling as claimed in claim 1 or 2, it is characterised in that the first extraction essence The inside for evaporating tower is filled with the double-level-metal screen waviness packings with diamond shape diversion window；Preferably, the inside of second extractive distillation column is filled with the double-level-metal screen waviness packings with diamond shape diversion window；Preferably, the First Heat Exchanger, second heat exchanger and the 3rd heat exchanger are each independently plate-type heat-exchange Device.
- 4. such as the system of the refined methyl cyclopentane of claims 1 to 3 any one of them recycling, it is characterised in that the solvent The extractant outlet of recovery unit is equipped with return pipeline, and the return pipeline sequentially passes through the 3rd heat exchanger, described second First extractive distillation column is connected after heat exchanger, the First Heat Exchanger.
- A kind of 5. method for recycling refined methyl cyclopentane, it is characterised in that the method is utilized as Claims 1 to 4 is any System described in carries out.
- 6. the method for the refined methyl cyclopentane of recycling as claimed in claim 5, it is characterised in that include the following steps：(1) after extractant and raw material containing methyl cyclopentane being carried out first time heating through First Heat Exchanger, first is introduced Extractive distillation column carries out first time rectifying extraction, overhead extraction light component；(2) step (1) remaining ingredient is carried out second from the bottom of towe of the first extractive distillation column through the second heat exchanger after heating up, into Enter to carry out second of rectifying extraction, overhead extraction methyl cyclopentane in the second extractive distillation column；(3) after step (2) remaining ingredient is from the bottom of towe of the second extractive distillation column through the progress third time heating of the 3rd heat exchanger, into Enter in solvent recovery unit and separated, obtain heavy constituent and extractant.
- 7. the method for the refined methyl cyclopentane of recycling as claimed in claim 6, it is characterised in that the extractant includes ring fourth Any one in sulfone, ethylene glycol, glycerine, N- N-formyl morpholine Ns, 1-methyl-2-pyrrolidinone and dimethylformamide or at least two The combination of kind, the mixed solvent formed with eutectic solvent compounding；Preferably, the eutectic solvent includes hydrogen bond receptor and hydrogen bond donor；Preferably, the hydrogen bond receptor includes tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutyl iodate Ammonium, tetrabutyl fluorination phosphorus, tetrabutyl phosphorus chloride, tetrabutyl phosphonium bromide phosphorus, tetrabutyl iodate phosphorus, choline chloride, glycine betaine, benzyl chloride In base triethyl ammonium and hydrogen sulfate tetrabutylammonium any one or at least two combination；Preferably, the hydrogen bond donor include formamide, acetamide, propionamide, ethylene glycol, propane diols, glycerine, isopropanol, Hexylene glycol, sorbierite, butanediol, glycolic, malic acid, lactic acid, citric acid, maleic acid, aconitic acid, levulic acid, urea, third Diureide, thiocarbamide, lysine, tryptophan, phenylalanine, methionine, threonine, isoleucine, leucine, valine, third Propylhomoserin, glutamic acid, asparatate, glycine, cystine, proline, tyrosine, serine, glucose, fructose, xylose, sugarcane Sugar and any one in maltose or at least two combination；Preferably, the molar ratio of hydrogen bond receptor described in the eutectic solvent and the hydrogen bond donor is 1:(1~10)；Preferably, the eutectic solvent is stirred to saturating at 80 DEG C~100 DEG C by the hydrogen bond receptor with the hydrogen bond donor It is bright and obtain；Preferably, the proportion of eutectic solvent described in the extractant is 1~30wt%；Preferably, the mass ratio of the extractant and the raw material is (2~6):1.
- 8. the method for refined methyl cyclopentane is recycled as described in any one of claim 5~7, it is characterised in that first extraction 1~2MPa of pressure of rectifying column is taken, column bottom temperature is 100~120 DEG C, and tower top temperature is 20~30 DEG C；Preferably, the pressure of second extractive distillation column is 1~2MPa, and column bottom temperature is 120~160 DEG C, and tower top temperature is 70~90 DEG C；Preferably, the pressure of the rectifying column is 1~2MPa, and column bottom temperature is 200~240 DEG C, and tower top temperature is 80~100 ℃。
- 9. the method for refined methyl cyclopentane is recycled as described in any one of claim 5~8, it is characterised in that first extraction The reflux ratio for taking rectifying column is 0.1~0.5, preferably 0.2~0.3；Preferably, the reflux ratio of second extractive distillation column is 5~10, preferably 7~8；Preferably, the reflux ratio of the rectifying column is 1~2, preferably 1.2~1.6；Preferably, extractant obtained by step (4) returns to first extractive distillation column after being cooled down through heat exchange unit.
- 10. the purposes of the method for refined methyl cyclopentane is recycled as described in claim 5~9, it is characterised in that the method is used The purification methyl cyclopentane in Aromatic raffinate, Cyclohexanone Production accessory substance fuel oil, cyclohexanol production accessory substance.
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| CN114152691A (en) * | 2021-11-26 | 2022-03-08 | 黄河三角洲京博化工研究院有限公司 | Method for analyzing contents of cyclopentane and extractant by gas chromatography |
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| CN115536488A (en) * | 2022-09-21 | 2022-12-30 | 黄河三角洲京博化工研究院有限公司 | Method for separating cyclopentane and 2,2-dimethylbutane by using eutectic solvent |
| CN115536488B (en) * | 2022-09-21 | 2024-05-28 | 黄河三角洲京博化工研究院有限公司 | Method for separating cyclopentane and 2, 2-dimethylbutane by eutectic solvent |
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Effective date of registration: 20201113 Address after: 341003 No.36, Huangjin Avenue, Ganzhou economic and Technological Development Zone, Ganzhou City, Jiangxi Province Patentee after: Jiangxi Rare Earth Research Institute, Chinese Academy of Sciences Address before: 100190 Beijing, Zhongguancun, north of No. two, No. 1, No. Patentee before: Institute of Process Engineering, Chinese Academy of Sciences |