CN114656332A - Composition, preparation method and application thereof - Google Patents
Composition, preparation method and application thereof Download PDFInfo
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- CN114656332A CN114656332A CN202011530258.4A CN202011530258A CN114656332A CN 114656332 A CN114656332 A CN 114656332A CN 202011530258 A CN202011530258 A CN 202011530258A CN 114656332 A CN114656332 A CN 114656332A
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- hydrogen bond
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- 239000000203 mixture Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 44
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 238000000895 extractive distillation Methods 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 amide compounds Chemical class 0.000 claims abstract description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 8
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 63
- 239000003795 chemical substances by application Substances 0.000 claims description 28
- 238000010992 reflux Methods 0.000 claims description 17
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 16
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 2
- 235000019743 Choline chloride Nutrition 0.000 claims description 2
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 2
- 229960003178 choline chloride Drugs 0.000 claims description 2
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 claims description 2
- UYDJAHJCGZTTHB-UHFFFAOYSA-N cyclopentane-1,1-diol Chemical compound OC1(O)CCCC1 UYDJAHJCGZTTHB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- WEAYWASEBDOLRG-UHFFFAOYSA-N pentane-1,2,5-triol Chemical compound OCCCC(O)CO WEAYWASEBDOLRG-UHFFFAOYSA-N 0.000 claims description 2
- ODTSDWCGLRVBHJ-UHFFFAOYSA-M tetrahexylazanium;chloride Chemical compound [Cl-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC ODTSDWCGLRVBHJ-UHFFFAOYSA-M 0.000 claims description 2
- 238000000605 extraction Methods 0.000 abstract description 39
- 239000007788 liquid Substances 0.000 abstract description 10
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 229940083957 1,2-butanediol Drugs 0.000 description 17
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 17
- 238000000926 separation method Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- CMMOAOWGVNAZKH-UHFFFAOYSA-N butane-1,2-diol ethane-1,2-diol Chemical compound C(C(CC)O)O.C(CO)O CMMOAOWGVNAZKH-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NZXNIRRRIOMHIE-UHFFFAOYSA-N 2,4,5-trimethyl-1h-imidazole;hydrochloride Chemical compound Cl.CC1=NC(C)=C(C)N1 NZXNIRRRIOMHIE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/84—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by extractive distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
- B01D3/40—Extractive distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the field of extractive distillation and discloses a composition, a preparation method and application thereof, wherein the composition comprises a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is selected from at least one of organic acid, alcohol and amide compounds; the hydrogen bond acceptor is at least one selected from quaternary ammonium salts. The composition has the characteristics of wide liquid process, low volatility, no toxicity, no harm, good biocompatibility, biodegradability and easy preparation, and the purity and yield of the first component and the second component obtained after extraction and rectification are more than 99.9 percent (weight).
Description
Technical Field
The invention relates to the field of extractive distillation, in particular to a composition, a preparation method and application thereof.
Background
Ethylene glycol is an important chemical raw material and is widely used in the industries of pesticides, medicines, petroleum and the like. The excellent properties of ethylene glycol have attracted much attention, and the production methods of ethylene glycol mainly include two major types, i.e., petroleum route and non-petroleum route. Ethylene glycol produced by petroleum ethylene process has three main production processes, namely Ethylene Oxide (EO) hydration process, ethylene glycol synthesis process by using ethylene oxide as intermediate and ethylene glycol coproduction dimethyl carbonate process. The non-petroleum route has two major production processes, namely, direct synthesis and indirect synthesis. The direct synthesis method is the simplest and most effective method, but the direct method has harsh reaction conditions, needs a high-temperature and high-pressure catalyst, is very expensive in rhodium catalyst, generates a large amount of by-product formate, and has low reaction conversion rate and selectivity, so the direct synthesis method is not widely popularized and applied. The indirect synthesis method is that firstly, synthetic gas is prepared by coal gasification, then dimethyl oxalate is synthesized by the synthetic gas, and then ethylene glycol is synthesized by further reaction, and the process is mostly adopted in domestic construction at present. However, when ethylene glycol is produced indirectly, the 1, 2-butanediol and ethylene glycol as by-products are azeotroped and distilled off from the top of the column, resulting in low purity and yield of ethylene glycol.
In recent years, extractive distillation is often used for separating ethylene glycol-1, 2-butanediol azeotropic mixtures. As a separation means commonly used in the chemical industry, extractive distillation achieves the separation purpose by adding a third component to change the relative volatility of the separated components, and the added third component is called an extractant. Although the extractant can effectively separate mixtures by increasing the relative volatility between azeotropic mixtures or breaking the azeotropic points between components, it generally has a higher boiling point and requires higher energy for the recovery process. Therefore, in addition to the selectivity of the extractant, the energy consumption and the economy of the separation process must be considered in the selection of the extractant. Many documents have studied about this azeotropic mixture, and for example, an organic solvent is used as an extractant, but the extractant has disadvantages of high solubility in the azeotropic mixture, volatility, high energy consumption for recovery, and the like, and therefore, the amount of the extractant used is large and the handling is not easy. The ionic liquid as an extractant can overcome the defects of organic solvents, but has the problems of high raw material price, complex synthesis and the like, and the large-scale industrial application of the ionic liquid is limited.
Disclosure of Invention
The invention aims to solve the problems of high difficulty in separating an azeotropic mixture, high solubility of an extracting agent in the azeotropic mixture, high volatility and high energy consumption in recovery in the prior art, provides a composition, a preparation method and application thereof, the composition comprises a hydrogen bond donor and a hydrogen bond acceptor, has the characteristics of wide liquid process, low volatility, no toxicity, no harm, good biocompatibility, biodegradability and easy preparation, and in addition, the composition is capable of increasing the relative volatility of a second component of the azeotropic mixture, such as the relative volatility of ethylene glycol in an ethylene glycol-1, 2-butanediol system, the solvent ratio is reduced, the purity and the yield of the first component and the second component obtained after the extractive distillation are more than 99.9 percent by weight, and the composition can be recycled, so that continuous extraction, rectification and separation can be performed, the cost is saved, and the method can be applied to industrialization.
The inventor of the invention finds in experiments that the composition comprising the hydrogen bond donor and the hydrogen bond acceptor has the characteristics of wide liquid process, low volatility, no toxicity, no harm, good biocompatibility, biodegradability and easy preparation, can be used as an extractant of an azeotropic mixture, can be recycled, saves cost and can be industrially applied.
In order to accomplish the above object, the present invention provides, in one aspect, a composition comprising a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is selected from at least one of an organic acid, an alcohol, and an amide compound; the hydrogen bond acceptor is at least one selected from quaternary ammonium salts.
In a second aspect, the present invention provides a process for preparing the above composition, which comprises: the hydrogen bond donor and the hydrogen bond acceptor are mixed under stirring to obtain a composition.
In a third aspect, the present invention provides a process for separating an azeotropic mixture containing a first component and a second component, the second component being a lower alcohol having 2 to 4 carbon atoms, the process comprising: and contacting the azeotropic mixture with an extracting agent for extractive distillation to obtain a first component and an extract containing the extracting agent and the second component, wherein the extracting agent is the composition or the composition prepared by the method.
The method for preparing the composition is simple and convenient, is easy to operate and is convenient for industrial application.
The method for separating the azeotropic mixture, provided by the invention, can improve the relative volatility of the second component in the azeotropic mixture, such as the relative volatility of ethylene glycol in an ethylene glycol-1, 2-butanediol system, reduce the solvent ratio, ensure that the purity and the yield of the first component and the second component obtained after extraction and rectification are more than 99.9 percent (weight), and can also recycle the composition, thereby carrying out continuous extraction and rectification separation, saving the cost and being applicable to industrialization.
Drawings
Fig. 1 is a schematic view of the structure of a system for separating an azeotropic mixture according to an embodiment of the present invention.
Description of the reference numerals
1 extraction rectifying column, 2 flash tanks, 3 extraction rectifying column overhead condensers, 4 extraction rectifying column bottom reboilers, 5 flash tank top condensers, 6 extraction rectifying column overhead storage tanks, 7 flash tank top storage tanks and 8 reflux pumps.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The present invention provides a composition comprising a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is selected from at least one of an organic acid, an alcohol and an amide compound; the hydrogen bond acceptor is at least one selected from quaternary ammonium salts.
In some embodiments of the present invention, preferably, the organic acid has 6 to 10 carbon atoms, and more preferably at least one selected from the group consisting of n-hexanoic acid, n-decanoic acid, and n-heptanoic acid.
In some embodiments of the present invention, preferably, the alcohol has a carbon number of 2 to 5, more preferably a diol and/or a triol. Further preferably, the diol is at least one selected from the group consisting of triethylene glycol, propylene glycol, cyclohexanediol, and cyclopentanediol. Further preferably, the triol is at least one of glycerol, butanetriol and 1,2, 5-pentanetriol.
In some embodiments of the present invention, preferably, the amide compound has 1 to 3 carbon atoms, and more preferably at least one selected from urea, formamide, and acetamide.
In some embodiments of the present invention, preferably, the quaternary ammonium salt has the formula R1R2R3R4NX, wherein R1、R2、R3And R4The same or different and each independently selected from a hydrocarbyl group or a hydroxyhydrocarbyl group, more preferably an alkyl group having 2 to 6 carbon atoms or a hydroxyalkyl group having 2 to 6 carbon atoms. X is a halogen anion, more preferably selected from F, Cl, Br or I. Further preferably, the quaternary ammonium salt is selected from at least one of tetraethylammonium chloride, tetrahexylammonium chloride, tetrabutylammonium bromide and choline chloride.
In some embodiments of the invention, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is preferably 1-10:1, more preferably 1-5: 1, more preferably 1 to 3: 1.
in the invention, the optimized composition can further effectively separate the azeotrope, the purity and the yield of the compound at the top of the extractive distillation tower reach more than 99.9 percent (weight), the solvent can be recovered by adopting a flash tank in the solvent recovery stage, the energy consumption is reduced by more than 20 percent, and the equipment investment is reduced by more than 30 percent.
According to a preferred embodiment of the invention, the composition consists solely of the above ingredients.
In a second aspect, the present invention provides a process for preparing the above composition, which comprises: the hydrogen bond donor and the hydrogen bond acceptor are mixed under stirring to obtain a composition.
In some embodiments of the invention, the temperature of the mixing is preferably 70 to 130 ℃, more preferably 80 to 120 ℃ in order to further facilitate the dissolution of the hydrogen bond donor and the hydrogen bond acceptor.
According to a preferred embodiment of the present invention, the hydrogen bond donor and the hydrogen bond acceptor are mixed under stirring (rotation speed 200-.
In a third aspect, the present invention provides a method for separating an azeotropic mixture, the azeotropic mixture containing a first component and a second component, the second component being a lower alcohol having 2 to 4 carbon atoms, the method comprising: and contacting the azeotropic mixture with an extracting agent for extractive distillation to obtain a first component and an extract containing the extracting agent and the second component, wherein the extracting agent is the composition or the composition prepared by the method.
In some embodiments of the present invention, preferably, the second component is ethylene glycol and/or propylene glycol.
In the present invention, an azeotropic mixture is a mixture of two or more different components in a homogeneous solution having only one boiling point at a constant pressure when the two or more different components are mixed in a specific ratio, and the mixture is an azeotropic mixture.
In the present invention, the kind of the first component is not particularly limited as long as it can form an azeotropic mixture with the second component.
In the present invention, the composition is particularly useful for separating an azeotropic mixture of ethylene glycol and 1, 2-butanediol.
In some embodiments of the invention, the molar ratio of the first component to the second component in the azeotrope is preferably 1 to 5: 1.
in some embodiments of the invention, the weight ratio of the azeotrope to the extractant is preferably from 0.5 to 2: 1.
In some embodiments of the invention, the feed temperature of the azeotrope is preferably in the range of 40 to 50 ℃. The feed temperature of the extractant is preferably 60 to 80 ℃.
In the present invention, the feeding volume flow rate of the azeotropic mixture is preferably 100-500L/h.
In some embodiments of the invention, the reflux ratio of the extractive distillation is preferably 3 to 10. The reflux ratio refers to the ratio of the flow L of reflux liquid returned from the top of the extraction rectification tower to the flow D of a product at the top of the tower, namely R is L/D, wherein L: liquid refluxed from the overhead condenser per unit time, unit: kmol/h. D: the distillate (product) extracted from the top of the rectification column in unit time has the unit: kmol/h. The reboiling ratio of the extractive distillation is preferably 1-5. The reboiling ratio is the ratio of the flow rate of a reflux liquid from a reboiler at the bottom of the tower to the amount of a kettle liquid (raffinate) led out from the bottom of the tower, namely R is L/W, wherein L: reflux liquid from the bottom reboiler per unit time, unit: kmol/h. W: the residue (raffinate) extracted from the bottom of the rectification column in unit time is as follows: kmol/h.
In the invention, during extraction and rectification, the first component is collected when the temperature at the tower top is 160-195 ℃, and the second component and the extract of the extracting agent are collected when the temperature at the tower bottom is 200-220 ℃.
In some embodiments of the invention, the method further comprises subjecting the extract to flash evaporation to separate the second component and the extractant. More preferably, the method further comprises the step of recycling the separated extractant to the extraction and rectification step so as to realize recycling of the extractant and save cost.
In some embodiments of the invention, the pressure of the flash is preferably 50 to 80 kPa. The temperature of the flash is preferably 150 ℃ to 200 ℃.
According to a preferred embodiment of the present invention, the extractive distillation of the azeotropic mixture is carried out using the system shown in FIG. 1. Specifically, an azeotropic mixture and an extracting agent (the weight ratio of the azeotropic mixture to the extracting agent is 0.5-2:1) are respectively added into an extraction and rectification tower 1, and a reboiler 4 at the bottom of the extraction and rectification tower is arranged at the bottom of the extraction and rectification tower so as to heat the kettle liquid extracted at the bottom of the tower. The feeding temperature of the azeotropic mixture is 40-50 ℃, the feeding temperature of the extracting agent is 60-80 ℃, the feeding volume flow of the azeotropic mixture is 500 plus of 100L/h, the reflux ratio of the extractive distillation is 3-10, the reboiling ratio of the extractive distillation is 1-5, when the tower top temperature of the extractive distillation tower 1 is 160 plus of 195 ℃, the first component obtained after the extractive distillation is condensed by a tower top condenser 3 of the extractive distillation tower, the first component is collected in a tower top storage tank 6 of the extractive distillation tower, when the tower bottom temperature is 200 plus of 220 ℃, the second component and the extracting agent are collected, and the extracting agent is conveyed to a flash tank 2 for flash evaporation, and the flash evaporation pressure is 50-80 kPa; the temperature of the flash evaporation is 150-.
In the present invention, the pressure is gauge pressure, and the room temperature is 25 ℃.
The present invention will be described in detail below by way of examples. In the examples and comparative examples, the reagents used were all commercially available analytical reagents.
Preparation example 1
Weighing hydrogen bond donor n-hexanoic acid and hydrogen bond acceptor tetrabutylammonium bromide (the molar ratio of the n-hexanoic acid to the tetrabutylammonium bromide is 1:1) in a container, heating the mixture of n-hexanoic acid and tetraethylammonium bromide at 80 ℃, stirring (stirring speed of 200 revolutions per minute) while heating, stopping heating after a clear transparent liquid is formed in the container, and stopping stirring when the temperature of the solution in the container is reduced to room temperature to obtain the composition.
Preparation example 2
A composition was prepared by the method of preparation 1 except that the molar ratio of n-hexanoic acid to tetrabutylammonium bromide was 2:1 and the heating temperature was 100 ℃.
Preparation example 3
A composition was prepared by the method of preparation example 1, except that the molar ratio of n-hexanoic acid to tetrabutylammonium bromide was 5:1, and the heating temperature was 120 ℃.
Preparation example 4
A composition was prepared according to the method of preparation 1, except that the hydrogen bond donor was urea and the hydrogen bond acceptor was tetrabutylammonium bromide.
Preparation example 5
A composition was prepared according to the method of preparation example 1, except that the hydrogen bond donor was glycerol and the hydrogen bond acceptor was tetraethylammonium chloride.
Example 1
Firstly, continuously adding 500L of azeotropic mixture into an extraction and rectification tower, wherein the azeotropic mixture is ethylene glycol-1, 2-butanediol (50 percent of ethylene glycol and 50 percent of 1, 2-butanediol are both in mole percentage), the feeding volume flow of the azeotropic mixture is 100L/h, the feeding temperature is 40 ℃, starting a heat source of the extraction and rectification tower and condensed water of a condenser, refluxing for a period of time after the temperature of the top of the extraction and rectification tower is stable, adding an extracting agent into the upper part of the extraction rectifying tower, wherein the extracting agent is the composition obtained in the preparation example 1, the feeding temperature of the extracting agent is 60 ℃, the weight ratio of the extracting agent to the azeotropic mixture is 0.5:1, when the tower top temperature of the extraction rectifying tower is 160 ℃, continuously extracting 1, 2-butanediol product from the top of the extractive distillation tower, controlling the reflux ratio to be 3 and the reboiling ratio at the bottom of the extractive distillation tower to be 2; when the temperature of the bottom of the extraction and rectification tower is 200 ℃, introducing the ethylene glycol-extractant distilled from the bottom of the extraction and rectification tower into a flash tank, wherein the operating pressure of the flash tank is 70kPa, the operating temperature is 150 ℃, cooling the 1, 2-butanediol obtained at the top of the flash tank by a cooler, then feeding the 1, 2-butanediol into a product tank, and refluxing the extractant distilled from the bottom of the flash tank to the extraction and rectification tower by a pump for recycling.
Example 2
Firstly, continuously adding 500L of azeotropic mixture into an extraction and rectification tower, wherein the azeotropic mixture is ethylene glycol-1, 2-butanediol (50% of ethylene glycol and 50% of 1, 2-butanediol which are mole percentages), the feeding volume flow of the azeotropic mixture is 100L/h, the feeding temperature is 45 ℃, starting a heat source of the extraction and rectification tower and condensed water of a condenser, refluxing for a period of time after the temperature of the top of the extraction and rectification tower is stable, adding an extracting agent into the upper part of the extraction rectifying tower, wherein the extracting agent is the composition obtained in the preparation example 2, the feeding temperature of the extracting agent is 70 ℃, the weight ratio of the extracting agent to the azeotropic mixture is 0.8:1, when the tower top temperature of the extraction rectifying tower is 170 ℃, continuously extracting 1, 2-butanediol product from the top of the extractive distillation tower, controlling the reflux ratio to be 5 and the reboiling ratio at the bottom of the extractive distillation tower to be 3; when the temperature of the bottom of the extraction and rectification tower is 210 ℃, introducing the ethylene glycol-extractant distilled from the bottom of the extraction and rectification tower into a flash tank, wherein the operating pressure of the flash tank is 75kPa, the operating temperature is 170 ℃, cooling the 1, 2-butanediol obtained at the top of the flash tank by a cooler, then feeding the 1, 2-butanediol into a product tank, and refluxing the extractant distilled from the bottom of the flash tank to the extraction and rectification tower by a pump for recycling.
Example 3
Firstly, continuously adding 500L of azeotropic mixture into an extraction and rectification tower, wherein the azeotropic mixture is ethylene glycol-1, 2-butanediol (50% of ethylene glycol and 50% of 1, 2-butanediol which are mole percentages), the feeding volume flow of the azeotropic mixture is 100L/h, the feeding temperature is 50 ℃, starting a heat source of the extraction and rectification tower and condensed water of a condenser, refluxing for a period of time after the temperature of the top of the extraction and rectification tower is stable, adding an extracting agent into the upper part of the extraction rectifying tower, wherein the extracting agent is the composition obtained in the preparation example 3, the feeding temperature of the extracting agent is 80 ℃, the weight ratio of the extracting agent to the azeotropic mixture is 1:1, when the tower top temperature of the extraction rectifying tower is 180 ℃, continuously extracting 1, 2-butanediol product from the top of the extractive distillation tower, controlling the reflux ratio to be 10 and the reboiling ratio at the bottom of the tower to be 5; when the temperature of the bottom of the extraction and rectification tower is 220 ℃, introducing the ethylene glycol-extractant distilled from the bottom of the extraction and rectification tower into a flash tank, wherein the operating pressure of the flash tank is 80kPa, the operating temperature is 200 ℃, cooling the 1, 2-butanediol obtained at the top of the flash tank by a cooler, then feeding the 1, 2-butanediol into a product tank, and refluxing the extractant distilled from the bottom of the flash tank to the extraction and rectification tower by a pump for recycling.
Example 4
The separation of the azeotropic mixture was carried out in the same manner as in example 1, except that the reboiling ratio was 2.5.
Example 5
The separation of the azeotropic mixture was carried out in the same manner as in example 1, except that the temperature of the flash distillation was 180 ℃ and the pressure was 50 kPa.
Example 6
The separation of the azeotrope was carried out according to the method of example 1, except that the molar ratio of n-hexanoic acid to tetrabutylammonium bromide was 10: 1.
example 7
The separation of the azeotropic mixture was carried out according to the method of example 1, except that the extractant was the composition obtained in preparation example 4.
Example 8
The separation of an azeotropic mixture was carried out by the same method as in example 1, except that the extractant was the composition obtained in preparation example 5.
Comparative example 1
The separation of the azeotrope was carried out as in example 1, except that triethylene glycol was used as the extractant.
Comparative example 2
The separation of the azeotrope was performed according to the method of example 1, except that the hydrogen bond donor used was levulinic acid.
Comparative example 3
The separation of the azeotrope was carried out according to the procedure of example 1, except that the hydrogen bond acceptor used was trimethylimidazole hydrochloride.
Test example 1
The purity and yield of the ethylene glycol and the 1, 2-butanediol obtained in the examples and the comparative examples are detected by gas chromatography, the adopted testing instrument is Agilent GC7890, and the specific detection method is as follows: a hydrogen flame ionization detector is adopted, the chromatographic column is AT-wax (30m multiplied by 0.53mm multiplied by 1 mu m), the temperature of the column box is 200 ℃, the temperature of the detector is 200 ℃, the temperature of the gasification chamber is 230 ℃, and the carrier gas is nitrogen. The test results obtained are shown in table 1.
TABLE 1
As can be seen from Table 1, when the compositions obtained in examples 1 to 6 and comparative examples 1 to 3 were used for separating an azeotropic mixture, the purity and yield of ethylene glycol in examples 1 to 6 and the purity and yield of 1, 2-butanediol were 99.9% by weight or more, and the purity and yield of ethylene glycol in comparative examples 1 to 3 and the purity and yield of 1, 2-butanediol were less than 99.9% by weight, indicating that the extraction of an azeotropic mixture using the composition of the present invention is effective and industrially advantageous.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (16)
1. A composition comprising a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is selected from at least one of an organic acid, an alcohol, and an amide compound; the hydrogen bond acceptor is at least one selected from quaternary ammonium salts.
2. The composition according to claim 1, wherein the organic acid has 6 to 10 carbon atoms, preferably at least one selected from the group consisting of n-hexanoic acid, n-decanoic acid and n-heptanoic acid.
3. Composition according to claim 1 or 2, wherein the alcohol has a number of carbon atoms from 2 to 5, preferably a diol and/or triol;
more preferably, the diol is selected from at least one of triethylene glycol, propylene glycol, cyclohexanediol, and cyclopentanediol;
more preferably, the triol is at least one of glycerol, butanetriol and 1,2, 5-pentanetriol.
4. The composition according to any one of claims 1 to 3, wherein the amide compound has 1 to 3 carbon atoms, and is preferably at least one selected from urea, formamide and acetamide.
5. The composition of any of claims 1-4, wherein the quaternary ammonium salt has the formula R1R2R3R4NX, wherein R1、R2、R3And R4Identical or different and each independently selected from alkyl or hydroxyalkyl, preferably alkyl of 2 to 6 carbon atoms or hydroxyalkyl of 2 to 6 carbon atoms, X is a halogen anion, preferably selected from F, Cl, Br or I; more preferably, the quaternary ammonium salt is selected from at least one of tetraethylammonium chloride, tetrahexylammonium chloride, tetrabutylammonium bromide and choline chloride.
6. The composition according to any one of claims 1 to 5, wherein the molar ratio of the hydrogen bond donor and the hydrogen bond acceptor is 1-10:1, preferably 1-5: 1, more preferably 1 to 3: 1.
7. a method of preparing the composition of any one of claims 1 to 6, comprising: the hydrogen bond donor and the hydrogen bond acceptor are mixed under stirring to obtain a composition.
8. The process according to claim 7, wherein the temperature of the mixing is 70-130 ℃, preferably 80-120 ℃.
9. A process for separating an azeotropic mixture containing a first component and a second component, the second component being a lower alcohol having from 2 to 4 carbon atoms, the process comprising: contacting the azeotropic mixture with an extracting agent for extractive distillation to obtain a first component and an extract containing the extracting agent and the second component, wherein the extracting agent is the composition of any one of claims 1 to 6 or the composition prepared by the method of any one of claims 7 to 8.
10. The method of claim 9, wherein the second component is ethylene glycol and/or propylene glycol.
11. The process according to claim 9 or 10, wherein the molar ratio of the first component to the second component in the azeotropic mixture is 1-5: 1.
12. the process of any one of claims 9-11, wherein the weight ratio of the azeotrope to the extractant is 0.5-2: 1.
13. The process of any one of claims 9-12, wherein the feed temperature of the azeotrope is 40-50 ℃; and/or the feed temperature of the extractant is 60 to 80 ℃.
14. The process according to any one of claims 9 to 13, wherein the extractive distillation has a reflux ratio of 3 to 10; the reboiling ratio of the extractive distillation is 1-5.
15. The process of any one of claims 9-14, wherein the process further comprises subjecting the extract to flash evaporation to separate the second component and the extractant.
16. The process of claim 15, wherein the pressure of the flash is 50-80 kPa; the temperature of the flash evaporation is 150-200 ℃.
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