CN105985213B - Method for screening alkane/cycloalkane system separation solvent - Google Patents
Method for screening alkane/cycloalkane system separation solvent Download PDFInfo
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- 239000002904 solvent Substances 0.000 title claims abstract description 269
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 190
- 150000001924 cycloalkanes Chemical class 0.000 title claims abstract description 167
- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000012216 screening Methods 0.000 title claims abstract description 44
- 238000000926 separation method Methods 0.000 title claims abstract description 27
- 239000012895 dilution Substances 0.000 claims abstract description 153
- 238000010790 dilution Methods 0.000 claims abstract description 153
- 230000000694 effects Effects 0.000 claims abstract description 150
- 239000000126 substance Substances 0.000 claims abstract description 64
- 125000000524 functional group Chemical group 0.000 claims abstract description 27
- 239000004020 conductor Substances 0.000 claims abstract description 13
- 238000004364 calculation method Methods 0.000 claims description 24
- 150000003254 radicals Chemical class 0.000 claims description 15
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- YKPQUSLRUFLVDA-UHFFFAOYSA-N $l^{2}-azanylmethane Chemical compound [NH]C YKPQUSLRUFLVDA-UHFFFAOYSA-N 0.000 claims description 3
- XXJGBENTLXFVFI-UHFFFAOYSA-N 1-amino-methylene Chemical compound N[CH2] XXJGBENTLXFVFI-UHFFFAOYSA-N 0.000 claims description 3
- TUCNEACPLKLKNU-UHFFFAOYSA-N acetyl Chemical compound C[C]=O TUCNEACPLKLKNU-UHFFFAOYSA-N 0.000 claims description 3
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000895 extractive distillation Methods 0.000 claims description 3
- 125000004005 formimidoyl group Chemical group [H]\N=C(/[H])* 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 claims description 3
- 125000004055 thiomethyl group Chemical group [H]SC([H])([H])* 0.000 claims description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 64
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 17
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 17
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical class CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 230000008569 process Effects 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011017 operating method Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 201000004569 Blindness Diseases 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GGBJHURWWWLEQH-UHFFFAOYSA-N butylcyclohexane Chemical compound CCCCC1CCCCC1 GGBJHURWWWLEQH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical class CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical group CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013178 mathematical model Methods 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- -1 pentamethylene, hexamethylene Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a screening method of a separation solvent of an alkane/cycloalkane system, belonging to the field of chemical separation. The method comprises the steps of firstly screening functional groups to synthesize a predetermined solvent; and acquiring the chemical potentials of the alkane and the cycloalkane in the solvent and pure components thereof by using a real solvent-like conductor shielding model. And obtaining infinite dilution activity coefficient theoretical values of the alkane and the cycloalkane in the solvent according to the obtained chemical potentials, and fitting the theoretical values to obtain the infinite dilution activity coefficient fitting values of the alkane and the cycloalkane. And obtaining an infinite dilution activity coefficient fitting value of a certain alkane and cycloalkane to be separated in a predetermined solvent according to the correlation, further obtaining the relative volatility of the alkane and cycloalkane in the predetermined solvent, calculating the solubility of the alkane and cycloalkane in the predetermined solvent on the premise that the relative volatility meets the requirement, and determining the predetermined solvent as a separation solvent if the solubility meets the requirement. The method provided by the embodiment of the invention is quick, simple, accurate and efficient.
Description
Technical field
The present invention relates to chemical separating field, more particularly to the screening technique of a kind of alkane/cycloalkane system separation solvent.
Background technology
Alkane/cycloalkane system is the common separation system of petrochemical industry.In the system, due to alkane and cycloalkanes
The boiling point of hydrocarbon is close, is also easy to produce nearly boiling or azeotropism, separating difficulty are high.And extracting rectifying is as a kind of point being simple and efficient
Separating process, by the way that separation solvent is added to close to the top of rectifying column, to change in feed liquid by relatively volatile between separation component
Degree makes the component (for example, nearly boiling point object system or azeotropic mixture system) that conventional distillation is difficult to detach become prone to detach.So at present
Generally use separation of extractive distillation technique detaches alkane/cycloalkane system under the action of suitably separation solvent.
It can be seen from the above, in the separation process of alkane/cycloalkane system, separation solvent plays an important role, it is necessary to screen one
The suitable solvent of kind.
Include to the screening criteria of the solvent used in the process of extracting rectifying at present：Selectivity, dissolubility, boiling point, density,
Surface tension, toxicity etc..Wherein, the selectivity and dissolubility of solvent are most important two standards.For the selectivity of solvent
For, refer to that the addition of solvent can be such that the relative volatility of component to be separated changes according to the direction of separation requirement.It is molten
Agent can selectively indicate that the higher selectivity for illustrating solvent of the relative volatility is more with the relative volatility between component to be separated
It is good, more it is conducive to the separation of component to be separated.For the dissolubility of solvent, it is expected that have between solvent and component to be separated compared with
High mutual solubility, to prevent liquid from generating lamination in tower.But in most cases, selectivity is better molten
Agent, dissolubility is lower, and vice versa.Therefore a kind of selectivity having had and high deliquescent solvent screening method are provided
It is particularly significant.
Currently, the screening technique of the separation solvent used in the process of extracting rectifying can substantially be divided into following four classes：
1) property leash law：It delimited needed for system to be separated according to certain principles (such as molecular structure and intermolecular force)
The approximate range of extractant is generally applied to the preliminary screening of solvent more.Subsequently need to also by other means to screening after
Solvent is further confirmed, cumbersome and less efficient.
2) activity coefficient method：By calculating the activity coefficient of system each component to be separated in a solvent, and then it is inferred to each
The relevant parameters such as selectivity, the dissolubility of selected extraction distillation solvent finally select suitable solvent by comparison.Since it is needed
Dilution activity coefficiet or limiting dilution activity coefficient are calculated by empirical model, need that needle is had according to different systems
Select property specific model, reliability unstable and less efficient.
3) computer optimization method：The solvent screening method that computer technology and Chemical Engineering Thermodynamics models coupling grow up.
It provides according to selective goal, is specifically chosen or is designed and finally obtains optimum solvent.Computer optimization method is broadly divided into meter
Two kinds of calculation machine aided molecular design method and computer optimization screening method, the two can be used in combination.Wherein, Computer-aided Molecular
Design method (CAMD) selects the molecular radical of certain structure in advance as needed first, then combines them according to certain rule
It is screened at molecule, and according to set solvent molecule destination properties, gradually reduces organic matter search range, eventually find
Required solvent.In addition, this method can also be reassembled into new solvent molecule to replace existing solvent, to obtain most
The economic benefit changed greatly.However, since CAMD methods are based on UNIFAC Group Contribution Methods, and UNIFAC Group Contribution Methods think
Each group role is mutual indepedent, the property of various substances can be calculated with the property of limited functional group, thus not
Isomer, kindred effect and the group system without fitting experimental data can be handled.
4) experimental method：By measuring the activity coefficient of Vapor -- Liquid Equilibrium Data or infinite dilute solution, calculate relatively volatile
Degree, the method to be screened to solvent.Equilibrium still method is mainly used due to measuring gas-liquid phase equilibrium data, for different
Separation system needs to change different equilibrium stills, and time-consuming and heavy workload.
Inventor has found that the prior art at least has following technical problem：
The screening technique that solvent is detached during the extracting rectifying that the prior art provides all has certain limitation, can not
Quickly, desired separation solvent simply, is accurately and efficiently filtered out.
Invention content
Technical problem to be solved of the embodiment of the present invention is, provides a kind of quick, simple, accurate and efficient alkane
The screening technique of hydrocarbon/cycloalkane system separation solvent.Specific technical solution is as follows：
An embodiment of the present invention provides the screening techniques that a kind of alkane/cycloalkane system detaches solvent, including：
Step a, backbone radical and functional group are screened from the synthesis group of solvent molecule, and utilize the backbone radical
Predetermined solvent is synthesized with the functional group；
Step b, using true solvent quasi-conductor screening model, the chemical potential, at least three kinds of of at least three kinds of alkane is calculated separately
The chemical potential and at least three kinds of cycloalkane of the chemical potential of cycloalkane, at least three kinds of alkane in the predetermined solvent
Chemical potential in the predetermined solvent obtains at least three kinds of alkane then according to dilution activity coefficiet calculation formula
Dilution activity coefficiet theoretical value and at least three kinds of cycloalkane in the predetermined solvent is in the predetermined solvent
Dilution activity coefficiet theoretical value；
Step c, the dilution activity coefficiet theoretical value by least three kinds of alkane in the predetermined solvent and described
Dilution activity coefficiet literature value of at least three kinds of alkane in the predetermined solvent is fitted, and obtains alkane described pre-
Determine the Empirical Equation of the dilution activity coefficiet match value in solvent；
Correspondingly, the dilution activity coefficiet theoretical value by least three kinds of cycloalkane in the predetermined solvent and
Dilution activity coefficiet literature value of at least three kinds of cycloalkane in the predetermined solvent is fitted, and obtains cycloalkane
The Empirical Equation of dilution activity coefficiet match value in the predetermined solvent；
Step d, determine alkane and cycloalkane to be separated respectively as the first alkane and the from alkane/cycloalkane system
One cycloalkane, obtain respectively first alkane and first cycloalkane chemical potential and they in the predetermined solvent
Chemical potential, and then obtain the infinite dilution in the predetermined solvent of first alkane and first cycloalkane respectively and live
Coefficient theoretical value is spent, then using dilution activity coefficiet match value of the alkane in the predetermined solvent through customs examination
The Empirical Equation of the dilution activity coefficiet match value of connection formula and the cycloalkane in the predetermined solvent, respectively
To the dilution activity coefficiet match value of first alkane and first cycloalkane in the predetermined solvent；
Step e, the infinite dilution activity according to first alkane and first cycloalkane in the predetermined solvent
Coefficient Fitting value obtains first alkane and first cycloalkane described predetermined using relative volatility calculation formula
Relative volatility in solvent；
Step f, when the relative volatility of first alkane and first cycloalkane in the predetermined solvent is more than
When equal to 1.2, step g is carried out；
When the relative volatility of first alkane and first cycloalkane in the predetermined solvent is less than 1.2,
Step a to step e is re-started, until first alkane and first cycloalkane waving relatively in the predetermined solvent
Hair degree is more than or equal to 1.2；
The step g includes：According to the chemical potential of first alkane and first cycloalkane and they described
Chemical potential in predetermined solvent respectively obtains first alkane and first cycloalkane exists using Calculation of Solubility formula
Solubility in the predetermined solvent, when the solubility of first alkane and first cycloalkane in the predetermined solvent
Be all higher than equal to 0.3g/g solvents when, determine the predetermined solvent be separation first alkane and first cycloalkane it is molten
Agent.
Specifically, in the step a, the synthesis group of the solvent molecule is made of backbone radical and functional group；
The backbone radical includes：CH3、CH2、CH、C、Cy-CH2、Cy-CH、Cy-C、ACH、AC、ACCH3、ACCH2Or
ACCH, wherein Cy is cycloalkyl group, and A is phenyl；
The functional group includes：OH、CH3CO、CH2CO、CH3COO、CH2COO、HCOO、CH-O、CH2NH2、CHNH2、
CHNH2、CN、CNH2、CH3NH、CH2NH、CHNH、CH3N、CH2N、CH2CN、COOH、CH2NO2、CH2SH、HCON(CH2)2、CON
(CH3)2、CON(CH2)2、CON(CH2)CH、CONHCH3、Cy-CH2OCH2、Cy-CONCH3、Cy-CONCH2、Cy-CONCH、Cy-
CONC、ACOH、ACNH2, ACH-N=ACH, AC-N=ACH or AC-N=AC, wherein Cy is cycloalkyl group, and A is phenyl.
Specifically, in the predetermined solvent, the number of the functional group is 1 or 2.
Specifically, in the step b, the dilution activity coefficiet calculation formula is：
Wherein, γiFor the dilution activity coefficiet theoretical values of component i in a solvent,In a solvent for component i
Chemical potential,For the chemical potential of component i, R is gas constant：8.314J/molK, T are temperature, unit K.
It specifically,, will be described unlimited using the dilution activity coefficiet theoretical value as abscissa in the step c
Activity coefficient literature value is diluted as abscissa, and the fitting is carried out by least square method, obtains the infinite dilution activity
The Empirical Equation of Coefficient Fitting value；
The Empirical Equation of the dilution activity coefficiet match value is：
Wherein, a, b, c, d, e are to be fitted determining constant by described,It lives for the infinite dilutions of component i in a solvent
Coefficient theoretical value is spent,For the dilution activity coefficiet match values of component i in a solvent.
Specifically, in the step e, the relative volatility calculation formula is：
Wherein, αijFor the relative volatility of component i and component j in a solvent,For the nothings of component i in a solvent
Limit dilution activity coefficient match value,For the saturated vapour pressure of component i,For the infinite dilutions of component j in a solvent
Activity coefficient match value,For the saturated vapour pressure of component j.
Specifically, the Calculation of Solubility formula is：
Wherein, xiFor the solubility of component i in a solvent,For the chemical potential of component i,In a solvent for component i
Chemical potential, Δ Gi,fusionFor 0, R it is gas constant when liquid phase for the melting free energy of component i：8.314J/molK T is
Temperature, unit K.
The advantageous effect that technical solution provided in an embodiment of the present invention is brought is：
The screening technique of alkane provided in an embodiment of the present invention/cycloalkane system separation solvent, by using backbone radical
Predetermined solvent is synthesized with functional group.Then alkane/cycloalkane system at least 3 is calculated using true solvent quasi-conductor screening model
The chemical potential of kind of alkane and at least three kinds of cycloalkane and their chemical potentials in predetermined solvent, to be lived according to infinite dilution
Degree coefficient formulas obtains the infinite dilution coefficient reason of above-mentioned at least three kinds of alkane and at least three kinds of cycloalkane in predetermined solvent
By value, the corresponding infinite dilution coefficient of above-mentioned at least three kinds of alkane and at least three kinds of cycloalkane in predetermined solvent is then recycled
Literature value is fitted, and obtains the experience of the dilution activity coefficiet match value of alkane and cycloalkane in predetermined solvent respectively
Correlation.It determines to need specific a kind of alkane to be separated and a kind of cycloalkane from alkane/cycloalkane system, respectively as
First alkane and the first cycloalkane obtain the nothing of the first alkane and the first cycloalkane in above-mentioned predetermined solvent according to the above method
Limit dilution activity coefficient theoretical value, and the infinite dilution according to obtained alkane and cycloalkane in the predetermined solvent is lived respectively
The Empirical Equation for spending Coefficient Fitting value, obtains the match value of the first alkane and the first cycloalkane in the predetermined solvent, in turn
Obtain the relative volatility of the first alkane and the first cycloalkane in the predetermined solvent.It is wanted ensuring that the relative volatility meets
Under the premise of asking, the solubility of the first alkane and the first cycloalkane in the predetermined solvent is calculated separately, when obtained solubility
When also meeting the requirements, you can determine the predetermined solvent can as the first alkane and the first cycloalkane separation of extractive distillation it is molten
Agent.
It can be seen from the above, method provided in an embodiment of the present invention, in a first aspect, functional group tentatively ensure it is synthesized
Predetermined solvent has desired polarity, the blindness and one-sidedness of solvent primary dcreening operation is avoided, to improve solvent screening efficiency.Second
Aspect, used true solvent quasi-conductor screening model can calculate all organic solvent and its isomer.Even if lacking
Few related component, the information of component can be also obtained by quantum chemistry calculation, is then calculated again by the model.Therefore, phase
Than in Group Contribution Methods such as UNIFAC, the applicable dicyandiamide solution of present invention institute is more extensive.The third aspect, obtained alkane
It can be suitable for most alkane with the Empirical Equation of dilution activity coefficiet match value of the cycloalkane in predetermined solvent
Hydrocarbon and cycloalkane, so the infinite dilution activity of different alkane and different cycloalkane in the predetermined solvent can be obtained easily
Coefficient Fitting value.Moreover, being fitted by using dilution activity coefficiet literature value, dilution activity coefficiet fitting
The reliability of value with it is almost the same using the obtained data of test method.So avoid it is cumbersome to each different alkane and
Cycloalkane is tested, and time and the expense of solvent screening are reduced, more quickly, sieve that is simple and further improving solvent
Select efficiency.Fourth aspect, the present invention improve solvent screening by the solubility of solvent and selectively as the standard of solvent screening
Accuracy.Moreover, in order to avoid unnecessary operation, it is molten that solvent is just carried out under the premise of the selectivity of solvent is met the requirements
The deterministic process of Xie Du more conducively improves the efficiency of solvent screening.
Description of the drawings
To describe the technical solutions in the embodiments of the present invention more clearly, make required in being described below to embodiment
Attached drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments of the invention, for
For those of ordinary skill in the art, without creative efforts, other are can also be obtained according to these attached drawings
Attached drawing.
Fig. 1-1 is dilution activity coefficiet matched curve figure of the alkane of the offer of the embodiment of the present invention 1 in acetonitrile；
Fig. 1-2 is dilution activity coefficiet matched curve figure of the cycloalkane of the offer of the embodiment of the present invention 1 in acetonitrile；
Fig. 2 is that the infinite dilution of the alkane and cycloalkane of the offer of the embodiment of the present invention 2 in n,N-Dimethylformamide is lived
Spend Coefficient Fitting curve graph；
Fig. 3 is the infinite dilution activity of the alkane and cycloalkane of the offer of the embodiment of the present invention 3 in N-Methyl pyrrolidone
Coefficient Fitting curve graph；
Fig. 4 is the dilution activity coefficiet fitting of the alkane and cycloalkane of the offer of the embodiment of the present invention 4 in ethylene glycol
Curve graph；
Fig. 5 is that the dilution activity coefficiet of the alkane and cycloalkane of the offer of the embodiment of the present invention 5 in diethylene glycol is quasi-
Close curve graph.
Specific implementation mode
To keep technical scheme of the present invention and advantage clearer, below in conjunction with attached drawing to embodiment of the present invention make into
One step it is described in detail.
Unless otherwise defined, all technical terms used in the embodiment of the present invention all have usual with those skilled in the art
The identical meaning understood.Before embodiment of the present invention is described further in detail, to understanding the embodiment of the present invention
Some terms provide definition.
1) in the embodiment of the present invention, " alkane " refers to alkane.
2) in the embodiment of the present invention, " chemical potential of alkane ", that " chemical potential of cycloalkane " refers respectively to alkane is pure
The chemical potential of component and the chemical potential of cycloalkane pure component.
3) in the embodiment of the present invention, " the dilution activity coefficiet match value of the alkane in (described) predetermined solvent
Empirical Equation " refer to the empirical correlation of dilution activity coefficiet match value of a kind of alkane in predetermined solvent
Formula is applicable to calculate a variety of different alkanes dilution activity coefficiet match value in predetermined solvent.Similarly, institute
Stating " Empirical Equation of dilution activity coefficiet match value of the cycloalkane in (described) predetermined solvent " has similar contain
Justice.
4) " the dilution activity coefficiet literature value " described in the embodiment of the present invention refers to being provided according to the prior art
Document or other information channel disclosed in some different specific alkane recognized by this field or cycloalkane described pre-
Determine the dilution activity coefficiet empirical value in solvent, those skilled in the art can be easily by consulting related art
It obtains.
5) " the first alkane " described in the embodiment of the present invention refers to a kind of optional alkane for belonging to paraffinic,
Without specific meaning, applied during may or may not be calculating chemical potential of the embodiment of the present invention
Any one in " alkane at least 3 ".Similarly, " the first cycloalkane " has similar meaning.
An embodiment of the present invention provides the screening techniques that a kind of alkane/cycloalkane system detaches solvent, include the following steps：
Step 101 screens backbone radical and functional group from the synthesis group of solvent molecule, and utilizes the skeleton base
Group and the functional group synthesize predetermined solvent.
The embodiment of the present invention carries out primary dcreening operation, the functional group of first choice selection solvent molecule, by work(by step 101 to solvent
Energy group primarily determines that there is synthesized solvent desired can change to interact between alkane and cycloalkane to be separated
The polarity of power avoids the blindness and one-sidedness of solvent primary dcreening operation, to improve solvent screening efficiency.
Specifically, the synthesis group of the solvent molecule described in the embodiment of the present invention is by backbone radical and functional group group
Include at, wherein backbone radical：CH3、CH2、CH、C、Cy-CH2、Cy-CH、Cy-C、ACH、AC、ACCH3、ACCH2Or ACCH,
Wherein, Cy is cycloalkyl group, and A is phenyl；Functional group includes：OH、CH3CO、CH2CO、CH3COO、CH2COO、HCOO、CH-O、
CH2NH2、CHNH2、CHNH2、CN、CNH2、CH3NH、CH2NH、CHNH、CH3N、CH2N、CH2CN、COOH、CH2NO2、CH2SH、
HCON(CH2)2、CON(CH3)2、CON(CH2)2、CON(CH2)CH、CONHCH3、Cy-CH2OCH2、Cy-CONCH3、Cy-CONCH2、
Cy-CONCH、Cy-CONC、ACOH、ACNH2, ACH-N=ACH, AC-N=ACH or AC-N=AC, wherein Cy is cycloalkyl group,
A is phenyl.
By the way that the good backbone radical of preliminary screening and functional group are combined, you can synthesize scheduled solvent.Ability
For field technique personnel it is understood that in synthesized solvent, the number of functional group is generally 1 or 2.
Step 102, using true solvent quasi-conductor screening model, calculate separately at least three kinds of alkane chemical potential, at least 3
Chemical potential and at least three kinds of cycloalkane of the chemical potential, at least three kinds of alkane of kind cycloalkane in predetermined solvent are predetermined
Chemical potential in solvent obtains at least three kinds of alkane in predetermined solvent then according to dilution activity coefficiet calculation formula
Dilution activity coefficiet in predetermined solvent of dilution activity coefficiet theoretical value and at least three kinds of cycloalkane it is theoretical
Value.
" true solvent quasi-conductor screening model " described in the embodiment of the present invention that is, COSMO-RS, refer to this field
Common thermodynamical model can be《True solvent quasi-conductor screening model (COSMO-RS)》(Mu Tiancheng, chemical progress,
The 10th phase of volume 20) described in.For example, it can be the exploitation of COSMOlogic GmbH＆Co.KG companies
COSMOtherm softwares, those skilled in the art can carry out the simulation and calculating of Related Mathematical Models easily with it.
It is understood that calculating the chemistry of alkane or cycloalkane pure component using true solvent quasi-conductor screening model
Gesture and their chemical potentials in certain solvent are state of the art.Those skilled in the art by true solvent seemingly
Alkane pure component and/or the molecular formula of the solvent are inputted in conductor shielding model, you can be readily available above-mentioned each chemical potential.
In order to realize subsequent fit procedure, at least three kinds of (such as 3-10 kinds are chosen respectively from alkane/cycloalkane system
Deng) alkane and at least three kinds of cycloalkane carries out the calculating of chemical potential.Wherein it is preferred to selected alkane and cycloalkane such one
Class alkane and cycloalkane, their dilution activity coefficiet literature values in the predetermined solvent by those skilled in the art public affairs
Know.
Wherein, dilution activity coefficiet calculation formula is：
Wherein, γiFor the dilution activity coefficiet theoretical values of component i in a solvent,In a solvent for component i
Chemical potential,For the chemical potential of component i, R is gas constant：8.314J/ (molK), T are temperature (K).Art technology
Personnel are it is understood that the temperature T in calculation formula described in the embodiment of the present invention refers to the temperature of system.In the nothing
In limit dilution activity coefficient calculation formula, component i can be understood as referring to above-mentioned at least three kinds of alkane or at least three kinds of rings
Alkane.
Due to true solvent quasi-conductor screening model used by the embodiment of the present invention can calculate all organic solvents and
Its isomer.Even if the information of component can be obtained if lacking related component by quantum chemistry calculation, then again by the mould
Type is calculated.Therefore, compared to Group Contribution Methods such as UNIFAC, the applicable dicyandiamide solution of present invention institute is more extensive.
Step 103, the dilution activity coefficiet of at least three kinds of alkane in predetermined solvent that will be obtained in step 102
Theoretical value and dilution activity coefficiet literature value of at least three kinds of alkane in predetermined solvent are fitted, and are obtained alkane and are existed
The Empirical Equation of dilution activity coefficiet match value in predetermined solvent；
Correspondingly, the dilution activity coefficiet theoretical value by least three kinds of cycloalkane in the predetermined solvent and at least 3
Dilution activity coefficiet literature value of the kind cycloalkane in predetermined solvent is fitted, and obtains cycloalkane in predetermined solvent
The Empirical Equation of dilution activity coefficiet match value.
In order to improve the accuracy of required dilution activity coefficiet, step 103 is by using dilution activity coefficiet
Literature value is fitted acquisition dilution activity coefficiet with the dilution activity coefficiet theoretical value obtained in step 102 to be intended
Conjunction value.The reliability of the dilution activity coefficiet match value with it is almost the same using the obtained data of test method, avoid
Cumbersome experiment process reduces time and the expense of solvent screening, more quickly, sieve that is simple and further improving solvent
Select efficiency.
Specifically, the infinite dilution activity system by least three kinds of alkane (alternatively, at least three kinds of cycloalkane) in predetermined solvent
Number theoretical value is as abscissa, accordingly, by the nothing of at least three kinds of alkane (alternatively, at least three kinds of cycloalkane) in predetermined solvent
Limit dilution activity coefficient literature value is programmed by Matlab as abscissa, above-mentioned fitting is carried out using least square method
Journey obtains the Empirical Equation of the dilution activity coefficiet match value of alkane (alternatively, cycloalkane).
The Empirical Equation of the dilution activity coefficiet match value is：
Wherein, a, b, c, d, e are to be fitted determining constant by described,It lives for the infinite dilutions of component i in a solvent
Coefficient theoretical value is spent,For the dilution activity coefficiet match values of component i in a solvent.In the infinite dilution activity system
In the Empirical Equation of number match value, component i can be understood as referring to any one alkane or any one cycloalkane.
For example, it can also map in Origin softwares, and be obtained using the fitting of a polynomial function in the software
Above-mentioned a, b, c, d, e parameter is to get to the Empirical Equation of dilution activity coefficiet match value.
The dilution activity coefficiet match value of above-mentioned obtained alkane and cycloalkane in predetermined solvent through customs examination
Connection formula can be suitable for most alkane and cycloalkane, so any one different alkane and different rings can be obtained easily
Dilution activity coefficiet match value of the alkane in the predetermined solvent.Moreover, by using dilution activity coefficiet document
Value is fitted, the reliability of the dilution activity coefficiet match value with it is almost the same using the obtained data of test method.
So avoid it is cumbersome each different alkane and cycloalkane are tested, reduce time and the expense of solvent screening,
More quickly, screening efficiency that is simple and further improving solvent.
As it can be seen that the calculation formula of the above-mentioned dilution activity coefficiet match value for specific solvent, that is, alkane or ring
It need to be only fitted on the Empirical Equation of the dilution activity coefficiet of alkane system in a solvent primary, so that it may corresponding for calculating
Alkane or cycloalkane dilution activity coefficiet in the solvent of homologue or isomer match value, fill up real
The blank of data is tested, a large amount of time and expense can also be equally saved, there is important meaning for improving solvent screening efficiency
Justice.
Step 104, determined from alkane/cycloalkane system alkane and cycloalkane to be separated respectively as the first alkane and
First cycloalkane obtains the chemical potential and their chemical potentials in predetermined solvent of the first alkane and the first cycloalkane respectively,
And then the dilution activity coefficiet theoretical value of the first alkane and the first cycloalkane in predetermined solvent is obtained respectively, then utilize
The Empirical Equation and cycloalkane of dilution activity coefficiet match value of the alkane in predetermined solvent are in predetermined solvent
The Empirical Equation of dilution activity coefficiet match value respectively obtains the first alkane and the first cycloalkane in predetermined solvent
Dilution activity coefficiet match value.
In step 104, by determining alkane and cycloalkane to be separated respectively as first from alkane/cycloalkane system
Alkane and the first cycloalkane, to obtain the chemical potential of the first alkane, the chemical potential of the first cycloalkane, the first alkane in predetermined solvent
In chemical potential in predetermined solvent of chemical potential and the first cycloalkane.Then above-mentioned dilution activity coefficiet is utilized
Dilution activity coefficiet theoretical value and first cycloalkane of first alkane in predetermined solvent is calculated pre- in calculation formula
Determine the dilution activity coefficiet theoretical value in solvent.Then it is utilized respectively infinite dilution activity system of the alkane in predetermined solvent
The empirical correlation of dilution activity coefficiet match value of the Empirical Equation and cycloalkane of number match value in predetermined solvent
Formula accordingly obtains dilution activity coefficiet match value and first cycloalkane of first alkane in predetermined solvent predetermined molten
Dilution activity coefficiet match value in agent.
To be separated it is different from the first alkane and/or first it is, of course, also possible to repeatedly be determined from alkane/cycloalkane system
The alkane and cycloalkane of cycloalkane are as alkane and cycloalkane to be separated.And carry out similar operations described below.
Step 105, the dilution activity coefficiet match value according to the first alkane and the first cycloalkane in predetermined solvent,
Using relative volatility calculation formula, the relative volatility of the first alkane and the first cycloalkane in predetermined solvent is obtained.
Specifically, which is：
Wherein, αijFor the relative volatility of component i and component j in a solvent,For the nothings of component i in a solvent
Limit dilution activity coefficient match value,For the saturated vapour pressure of component i,For the infinite dilutions of component j in a solvent
Activity coefficient match value,For the saturated vapour pressure of component j.Wherein, component i and component j can be understood as distinguishing in the formula
Refer to the first alkane and the first cycloalkane.The saturated vapor pressure of component i and component j are definite value, can be by consulting chemical industry hand
Volume obtains.
Continue step 106 after having carried out step 105, in the embodiment of the present invention, step 106 include it is arbitrary select one into
Capable step 1061 and step 1062.
Step 1061 is：When the relative volatility of the first alkane and the first cycloalkane in predetermined solvent is more than or equal to 1.2
When, carry out step 107：According to the chemical potential of the first alkane and the first cycloalkane and their chemical potentials in predetermined solvent,
Using Calculation of Solubility formula, the solubility of the first alkane and the first cycloalkane in predetermined solvent is respectively obtained, when the first alkane
The solubility of hydrocarbon and the first cycloalkane in predetermined solvent is all higher than equal to 0.3g/g solvents, preferably greater than or equal to 0.5g/g solvents
When, determine that predetermined solvent is to detach the solvent of the first alkane and the first cycloalkane.
It is understood that the chemical potential of the first alkane and the first cycloalkane and their chemical potentials in predetermined solvent
Chemical potential of the chemical potential, the first alkane of the chemical potential, the first cycloalkane that refer to the first alkane in predetermined solvent, the first ring
Chemical potential of the alkane in predetermined solvent.Similarly, they are also to be obtained by using true solvent quasi-conductor screening model.
Specifically, Calculation of Solubility formula is：
Wherein, xiFor the solubility of component i in a solvent,For the chemical potential of component i,In a solvent for component i
Chemical potential, Δ Gi,fusionFor 0, R it is gas constant when liquid phase for the melting free energy of component i：8.314J/molK T is
Temperature, unit K.
Step 1062：When the relative volatility of the first alkane and the first cycloalkane in predetermined solvent is less than 1.2, again
Step 101 is carried out to step 105, until the relative volatility of the first alkane and the first cycloalkane in scheduled solvent again is big
In equal to 1.2.
As it can be seen that the embodiment of the present invention first judges the solubility of solvent by step 106, when the first alkane and
When relative volatility of one cycloalkane in predetermined solvent is more than or equal to 1.2, you can predetermined molten synthesized by indicating in step 101
The selectivity of agent is met the requirements.On this basis, you can carry out the judgement of the predetermined solvent solubility down.When the first alkane and
When relative volatility of first cycloalkane in predetermined solvent is less than or equal to 1.2, you can indicate synthesized in step 101 and make a reservation for
The selectivity of solvent is unsatisfactory for requiring, you can re-starts step 101 to step 105, until the first alkane and the first cycloalkane
Relative volatility in scheduled solvent again is more than or equal to 1.2.So that avoiding useless operating process, not only
Operating process is simplified, and improves the efficiency of solvent screening.
And there is excellent selectivity and solubility by ensureing predetermined solvent in step 107, by the solubility of solvent and
Selectively as the standard of solvent screening, the property for the solvent investigated is more accurate, improves the accuracy of solvent screening.
Method described in the embodiment of the present invention is suitable for detaching alkane/cycloalkane system with 4-12 carbon atom, excellent
Alkane/cycloalkane system of the choosing separation with 5-9 carbon atom.For example, which can be butane, 2- methyl fourths
The alkanes such as alkane, pentane, 2,2- dimethylbutanes, 2,3- dimethylbutanes, hexane.The cycloalkane can be pentamethylene, hexamethylene
The cycloalkane such as alkane, methyl cyclopentane, hexahydrotoluene, ethyl cyclohexane, butyl cyclohexane.
The present invention will be further described through by specific embodiment below.
Condition person is not specified in operating process in following specific examples, suggests according to normal condition or manufacturer
Condition carries out.It is raw materials used be not specified production firm and specification person be can be with conventional products that are commercially available.
Embodiment 1
The present embodiment screens backbone radical CH from the synthesis group of solvent molecule3With functional group CN, and utilize the bone
Frame group and functional group have synthesized predetermined solvent：Acetonitrile (CH3CN), and investigated whether acetonitrile can be used as alkane/cycloalkane
The separation solvent of system.Steps are as follows：
Using true solvent quasi-conductor screening model, the change of the chemical potential, a variety of cycloalkane of a variety of alkane has been calculated separately
It learns gesture and their chemical potentials in acetonitrile obtains a variety of alkane then according to dilution activity coefficiet calculation formula
With dilution activity coefficiet theoretical value of a variety of cycloalkane in acetonitrile.Infinite dilution of a variety of alkane in acetonitrile is lived
Coefficient theoretical value is spent as abscissa, accordingly, by the dilution activity coefficiet literature value of a variety of alkane in acetonitrile
As abscissa, above-mentioned fit procedure is carried out by origin softwares, obtains the dilution activity coefficiet match value of alkane
Empirical Equation.Matched curve such as Fig. 1-1 institutes of dilution activity coefficiet theoretical value and literature value of the alkane in acetonitrile
Show.Similarly, matched curve such as Fig. 1-2 of dilution activity coefficiet theoretical value and literature value of the cycloalkane in acetonitrile is obtained
It is shown.
Wherein, under conditions of 25 DEG C, above-mentioned various alkane and cycloalkane are in acetonitrile before dilution activity coefficiet fitting
Relative deviation afterwards is as shown in table 1：
The ln γ of alkane and cycloalkane in acetonitrile when 1 25 DEG C of table∞Fitness bias
As shown in Table 1, the mean relative deviation of above-mentioned various alkane and the cycloalkane dilution activity coefficiet in acetonitrile
Become from 22.78% before fitting 0.97% after being fitted, illustrates that the Empirical Equation can quickly be obtained with experiment value more
Close dilution activity coefficiet, to provide safeguard for the screening of solvent.
Determine that alkane and cycloalkane to be separated are respectively 2,2- dimethylbutanes and ring penta from alkane/cycloalkane system
Alkane, obtains the chemical potential and their chemical potentials in acetonitrile of 2,2- dimethylbutanes and pentamethylene respectively, and then obtains respectively
The dilution activity coefficiet theoretical value of 2,2- dimethylbutanes and pentamethylene in acetonitrile is taken, then utilizes alkane in acetonitrile
Dilution activity coefficiet match value Empirical Equation and cycloalkane in acetonitrile dilution activity coefficiet fitting
The Empirical Equation of value respectively obtains the dilution activity coefficiet match value of 2,2- dimethylbutanes and pentamethylene in acetonitrile
Respectively 16.11 and 25.57, the saturated vapour pressure of the two is respectively 42.33 and 42.74kPa, and 2,2- bis- is obtained to obtain calculating
The relative volatility of methybutane and pentamethylene in acetonitrile is 1.60, and selectivity is met the requirements.Then ring penta is calculated
The solubility of alkane and 2,2- dimethylbutanes in acetonitrile is respectively 0.064g/g solvents and 0.042g/g solvents.Consider phase
To volatility and solubility, for acetonitrile to pentamethylene and 2, the solubility property of 2- dimethylbutanes is poor, is easy in extracting rectifying
There is two-phase operation, therefore is not preferably solvent.
Embodiment 2
The operating procedure of the present embodiment is same as Example 1, is CON (CH difference lies in the functional group that area chooses3)2, close
At solvent molecule be n,N-Dimethylformamide (DMF).
Using the obtained alkane of method provided in an embodiment of the present invention and cycloalkane n,N-Dimethylformamide nothing
The matched curve of limit dilution activity coefficient theoretical value and literature value is as shown in Figure 2.Wherein, under conditions of 25 DEG C, various alkane and
Cycloalkane front and back relative deviation of dilution activity coefficiet fitting in DMF is as shown in table 2：
The ln γ of alkane and cycloalkane in DMF when 2 25 DEG C of table∞Fitness bias
The dilution activity coefficiet after over-fitting and literature value are more close as can be seen from Table 2.Utilize the present invention
Dilution activity coefficiet difference of the pentamethylene and 2,2- dimethylbutanes that the method that embodiment provides is calculated in DMF
Saturated vapour pressure for 8.46 and 15.38, the two is respectively 42.33 and 42.74kPa, is to which relative volatility be calculated
1.84。
Calculate the solubility of pentamethylene and 2,2- dimethylbutanes in DMF be respectively 0.439g/g solvents and
0.416g/g solvents.Consider relative volatility and solubility, DMF is to pentamethylene and 2, the solubility property of 2- dimethylbutanes
Preferably, also there is higher relative volatility, 1.84 can be reached, therefore, can be used as preferred solvent.
Embodiment 3
The operating procedure of the present embodiment is same as Example 1, is CON (CH difference lies in the functional group of selection2)2, synthesis
Solvent molecule be N-Methyl pyrrolidone (NMP), each alkane and cycloalkane N-Methyl pyrrolidone infinite dilution live
The literature value and theoretical value for spending coefficient obtain the Empirical Equation of dilution activity coefficiet match value as shown in figure 3, being fitted.It is quasi-
The relative deviation for closing front and back dilution activity coefficiet is shown in Table 3.
The ln γ of alkane and cycloalkane in NMP when 3 25 DEG C of table∞Fitness bias
As shown in Table 3, the dilution activity coefficiet after over-fitting and literature value are more close.Implemented using the present invention
Dilution activity coefficiet of the method pentamethylene and 2,2- dimethylbutanes that are calculated that example provides in NMP be respectively
7.69 and 12.73, the saturated vapour pressure of the two is respectively 42.33 and 42.74kPa, is to which relative volatility be calculated
1.67。
Calculate the solubility of pentamethylene and 2,2- dimethylbutanes in NMP be respectively 0.649g/g solvents and
0.629g/g solvents.Consider relative volatility and solubility, NMP is to pentamethylene and 2, the solubility property of 2- dimethylbutanes
Preferably, relative volatility can also reach 1.67, therefore also can be used as preferred solvent.
Embodiment 4
The operating procedure of the present embodiment is same as Example 1, is OH, the solvent of synthesis difference lies in the functional group of selection
Molecule is ethylene glycol, and the literature value and theoretical value of the dilution activity coefficiet of each alkane and cycloalkane in ethylene glycol are as schemed
Shown in 4, fitting obtains the Empirical Equation of dilution activity coefficiet match value.The phase of the front and back dilution activity coefficiet of fitting
4 are shown in Table to deviation.
The ln γ of alkane and cycloalkane in ethylene glycol when 4 25 DEG C of table∞Fitness bias
As shown in Table 4, the dilution activity coefficiet after over-fitting and literature value are more close.Implemented using the present invention
Dilution activity coefficiet of the method pentamethylene and 2,2- dimethylbutanes that are calculated that example provides in NMP be respectively
106.47 and 383.88, the saturated vapour pressure of the two is respectively 42.33 and 42.74kPa, is to which relative volatility be calculated
3.61。
Calculate the solubility of pentamethylene and 2,2- dimethylbutanes in NMP be respectively 0.047g/g solvents and
0.031g/g solvents.Consider relative volatility and solubility, ethylene glycol is to pentamethylene and 2, the dissolving of 2- dimethylbutanes
Performance is poor, two-phase operation is susceptible in extracting rectifying, therefore be not preferably solvent.
Embodiment 5
The operating procedure of the present embodiment is same as Example 1, is OH, the solvent of synthesis difference lies in the functional group of selection
Molecule is diethylene glycol, the literature value and theoretical value of the dilution activity coefficiet of each alkane and cycloalkane in diethylene glycol
As shown in figure 5, fitting obtains the Empirical Equation of dilution activity coefficiet match value.The front and back dilution activity coefficiet of fitting
Relative deviation be shown in Table 5.
The ln γ of alkane and cycloalkane in diethylene glycol when 5 25 DEG C of table∞Fitness bias
As shown in Table 5, the dilution activity coefficiet after over-fitting and literature value are more close.Implemented using the present invention
Dilution activity coefficiet of the method pentamethylene and 2,2- dimethylbutanes that are calculated that example provides in NMP be respectively
35.78 and 78.40, the saturated vapour pressure of the two is respectively 42.33 and 42.74kPa, is to which relative volatility be calculated
2.21。
Calculate the solubility of pentamethylene and 2,2- dimethylbutanes in NMP be respectively 0.092g/g solvents and
0.071g/g solvents.Consider relative volatility and solubility, ethylene glycol is to pentamethylene and 2, the dissolving of 2- dimethylbutanes
Performance is poor, two-phase operation is susceptible in extracting rectifying, therefore be not preferably solvent.
The foregoing is merely presently preferred embodiments of the present invention, the protection domain being not intended to limit the invention, all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.
Claims (7)
1. a kind of screening technique of alkane/cycloalkane system separation solvent, including：
Step a, backbone radical and functional group are screened from the synthesis group of solvent molecule, and utilize the backbone radical and institute
State functional group synthesis predetermined solvent；
Step b, using true solvent quasi-conductor screening model, the chemical potential of at least three kinds of alkane, at least three kinds of cycloalkanes are calculated separately
The chemical potential and at least three kinds of cycloalkane of the chemical potential of hydrocarbon, at least three kinds of alkane in the predetermined solvent are in institute
The chemical potential in predetermined solvent is stated, then according to dilution activity coefficiet calculation formula, obtains at least three kinds of alkane in institute
State the nothing of dilution activity coefficiet theoretical value and at least three kinds of cycloalkane in the predetermined solvent in predetermined solvent
Limit dilution activity coefficient theoretical value；
Step c, the dilution activity coefficiet theoretical value by least three kinds of alkane in the predetermined solvent and it is described at least
Dilution activity coefficiet literature value of 3 kinds of alkane in the predetermined solvent is fitted, and obtains alkane described predetermined molten
The Empirical Equation of dilution activity coefficiet match value in agent；
Correspondingly, the dilution activity coefficiet theoretical value by least three kinds of cycloalkane in the predetermined solvent and described
Dilution activity coefficiet literature value of at least three kinds of cycloalkane in the predetermined solvent is fitted, and obtains cycloalkane in institute
State the Empirical Equation of the dilution activity coefficiet match value in predetermined solvent；
Step d, determine alkane and cycloalkane to be separated respectively as the first alkane and the first ring from alkane/cycloalkane system
Alkane obtains chemical potential and their changes in the predetermined solvent of first alkane and first cycloalkane respectively
Gesture is learned, and then obtains the infinite dilution activity system of first alkane and first cycloalkane in the predetermined solvent respectively
Number theoretical value, then utilizes the Empirical Equation of dilution activity coefficiet match value of the alkane in the predetermined solvent
And the Empirical Equation of dilution activity coefficiet match value of the cycloalkane in the predetermined solvent, respectively obtain institute
State the dilution activity coefficiet match value of the first alkane and first cycloalkane in the predetermined solvent；
Step e, the dilution activity coefficiet according to first alkane and first cycloalkane in the predetermined solvent
Match value obtains first alkane and first cycloalkane in the predetermined solvent using relative volatility calculation formula
In relative volatility；
Step f, when the relative volatility of first alkane and first cycloalkane in the predetermined solvent is more than or equal to
When 1.2, step g is carried out；
When the relative volatility of first alkane and first cycloalkane in the predetermined solvent is less than 1.2, again
Step a to step e is carried out, until the relative volatility of first alkane and first cycloalkane in the predetermined solvent
More than or equal to 1.2；
The step g includes：According to the chemical potential of first alkane and first cycloalkane and they described predetermined
Chemical potential in solvent respectively obtains first alkane and first cycloalkane described using Calculation of Solubility formula
Solubility in predetermined solvent, when the solubility of first alkane and first cycloalkane in the predetermined solvent is big
When equal to 0.3g/g solvents, determine that the predetermined solvent is to detach the solvent of first alkane and first cycloalkane；
The separation solvent is separation of extractive distillation solvent.
2. according to the method described in claim 1, it is characterized in that, in the step a, the synthesis group of the solvent molecule by
Backbone radical and functional group composition；
The backbone radical includes：CH3、CH2、CH、C、Cy-CH2、Cy-CH、Cy-C、ACH、AC、ACCH3、ACCH2Or ACCH,
In, Cy is cycloalkyl group, and A is phenyl；
The functional group includes：OH、CH3CO、CH2CO、CH3COO、CH2COO、HCOO、CH-O、CH2NH2、CHNH2、CHNH2、
CN、CNH2、CH3NH、CH2NH、CHNH、CH3N、CH2N、CH2CN、COOH、CH2NO2、CH2SH、HCON(CH2)2、CON(CH3)2、
CON(CH2)2、CON(CH2)CH、CONHCH3、Cy-CH2OCH2、Cy-CONCH3、Cy-CONCH2、Cy-CONCH、Cy-CONC、
ACOH、ACNH2, ACH-N=ACH, AC-N=ACH or AC-N=AC, wherein Cy is cycloalkyl group, and A is phenyl.
3. according to the method described in claim 2, it is characterized in that, in the predetermined solvent, the number of the functional group is 1
Or 2.
4. according to the method described in claim 1, it is characterized in that, in the step b, the dilution activity coefficiet calculates
Formula is：
Wherein, γiFor the dilution activity coefficiet theoretical values of component i in a solvent,For the chemistry of component i in a solvent
Gesture,For the chemical potential of component i, R is gas constant：8.314J/molK, T are temperature, unit K.
5. according to the method described in claim 4, it is characterized in that, in the step c, the dilution activity coefficiet is managed
Be used as abscissa by value, using the dilution activity coefficiet literature value as abscissa, carried out by least square method described in
Fitting, obtains the Empirical Equation of the dilution activity coefficiet match value；
The Empirical Equation of the dilution activity coefficiet match value is：
Wherein, a, b, c, d, e are to be fitted determining constant by described,For the infinite dilution activity systems of component i in a solvent
Number theoretical value,For the dilution activity coefficiet match values of component i in a solvent.
6. according to the method described in claim 5, it is characterized in that, in the step e, the relative volatility calculation formula
For：
Wherein, αijFor the relative volatility of component i and component j in a solvent,For component i in a solvent unlimited dilute
Release activity coefficient match value, Pi SFor the saturated vapour pressure of component i,For the infinite dilution activity of component j in a solvent
Coefficient Fitting value,For the saturated vapour pressure of component j.
7. according to the method described in claim 6, it is characterized in that, the Calculation of Solubility formula is：
Wherein, xiFor the solubility of component i in a solvent,For the chemical potential of component i,For the changes of component i in a solvent
Learn gesture, Δ Gi,fusionFor 0, R it is gas constant when liquid phase for the melting free energy of component i：8.314J/molK, T are temperature,
Unit is K.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000044695A1 (en) * | 1999-01-28 | 2000-08-03 | Izak Nieuwoudt | Separation of methanol and methyl acetate from mixtures thereof by extractive distillation |
-
2015
- 2015-01-30 CN CN201510048289.9A patent/CN105985213B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000044695A1 (en) * | 1999-01-28 | 2000-08-03 | Izak Nieuwoudt | Separation of methanol and methyl acetate from mixtures thereof by extractive distillation |
Non-Patent Citations (2)
| Title |
|---|
| Measurement of Activity Coefficients at Infinite Dilution in Solvent Mixtures Using the Dilutor Technique;Michael Krummen等;《Ind. Eng. Chem. Res.》;20001231;第39卷;第2114-2123页 * |
| 萃取精馏溶剂筛选方法的评述;胡兴兰等;《承德石油高等专科学校学报》;20071231;第9卷(第3期);第7-10页 * |
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