CN104098463A - Separation method for benzene polycarboxylic acid isomers - Google Patents
Separation method for benzene polycarboxylic acid isomers Download PDFInfo
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C07C51/487—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to chemical modification
Abstract
The invention relates to a separation method for benzene polycarboxylic acid isomers. The method includes: adding a quaternary ammonium salt into a solution of benzene polycarboxylic acid isomers, conducting stirring, and making the quaternary ammonium salt interact with one of the benzene polycarboxylic acid isomers so as to form an eutectic mixture; filtering the formed eutectic mixture; drying the filtered eutectic mixture to remove the residual solvent from the eutectic mixture; mixing and stirring the dried eutectic mixture and a back extraction solvent, and performing filtering to obtain a quaternary ammonium salt containing back extraction solvent and one of the benzene polycarboxylic acid isomer; and distilling the quaternary ammonium salt containing back extraction solvent to recover the back extraction solvent and the quaternary ammonium salt.
Description
Technical field
The present invention relates to a kind of separation method of benzene polycarboxylic acid's isomers.
Background technology
Benzene polycarboxylic acid is important industrial chemicals, industrial, has a wide range of applications.As phthalic acid is used for producing dyestuff, vibrin, terylene, medicine and softening agent.M-phthalic acid is for the production of Synolac, unsaturated polyester resin and other superpolymer.Benzene tricarboxylic acid is for the preparation of resin, softening agent, dyestuff, linking agent etc.These benzene polycarboxylic acids are mainly obtained through catalyzed oxidation by its corresponding aromatic hydrocarbons at present, and these aromatic hydrocarbons directly or indirectly obtain from oil.China's oil resource is relatively deficient, and coal is relatively rich, therefore from coal benzene polycarboxylic acid processed by significant.But the product being obtained by oxidation of coal is a complicated benzene polycarboxylic acid's mixture, in these mixtures, there is again isomers to exist.Therefore how separation of benzene poly carboxylic acid isomers becomes the key issue that is made benzene polycarboxylic acid by oxidation of coal.Therefore the separation method of, developing a kind of benzene polycarboxylic acid's isomers of energy-saving and environmental protection has great importance.
The separation method of traditional isomers is mainly column chromatography for separation method, the method be a kind of can the method for separated isomers.As used the separated carotenoid isomers of performance liquid chromatographic column (Hongyan Li, Zeyuan Deng, Ronghua Liu, Steven Loewen, Rong Tsao. Ultra-performance liquid chromatographic separation of geometric isomers of carotenoids and antioxidant activities of 20 tomato cultivars and breeding lines. Food Chemistry, 2012,132 (1): 508 – 517); With the separated hydroxy-isoflavone isomers of performance liquid chromatographic column (Weina Liu, Jianguang Luo, Lingyi Kong. Application of complexation high-speed counter-current chromatography in the separation of 5-hydroxyisoflavone isomers from Belamcanda chinensis (L.) DC. Journal of Chromatography A, 2011,1218 (14): 1842 – 1848).But column chromatography for separation complicated operation, require strict, use a large amount of organic solvents, energy consumption is large, equipment is expensive with filler, investment greatly, single fractional dose is few, yield poorly, and can not meet the industrial demand to benzene polycarboxylic acid.Therefore need a kind of method of new efficient separation of benzene poly carboxylic acid isomers.
Eutectic method separated aspect, had at present report use quaternary ammonium salt can be by the aldehydes matter in coal tar the mode extracting and separating by forming low eutectic solutions out, and percentage extraction is also higher.Also there is in addition report quaternary ammonium salt to form low eutectic solutions phenomenon with some small molecules carboxylic acids.The fusing point of these low eutectic solutions is generally very low, is far smaller than room temperature.Its principle is that phenol or carboxylic acid are hydrogen bond donor, and quaternary ammonium salt is hydrogen bond receptor, and the effect between hydrogen bond receptor and hydrogen bond donor has reduced the lattice energy between the ion of quaternary ammonium salt, thereby made melting point depression.But these separation are at present all to form liquid eutectic mixture.If form solid eutectic mixture, also can produce hydrogen bond donor because the locus of hydrogen bond is different, the chemical stability of the eutectic mixture forming is different, lattice energy is different, cause the difference of reactive force between the different hydrogen bond donor structure in hydrogen bond locus and hydrogen bond receptor (quaternary ammonium salt), thereby realize the selective separation of isomers.Method of the present invention is with traditional separated difference of eutectic method: forming eutectic mixture is solid, utilize the sterically hindered characteristic of isomers, isomers sequencing when forming eutectic mixture is different, thereby realizes the high efficiency separation of benzene polycarboxylic acid's isomers.
Summary of the invention
The object of the invention is to solve a difficult problem for current benzene polycarboxylic acid's isomers separation.With the quaternary ammonium salt of recyclable regeneration and benzene polycarboxylic acid, form eutectic mixture (also claiming " eutectic solid mixture ") and carry out separation of benzene poly carboxylic acid isomers, belong to selective extraction separation.Method separation efficiency of the present invention is high, can process on a large scale, can meet the industrial mass-produced demand to benzene polycarboxylic acid.
Above-mentioned purpose of the present invention adopts following technical scheme to realize.
A separation method for benzene polycarboxylic acid's isomers, the method comprises the steps:
(1) in the solution of benzene polycarboxylic acid's isomers, add quaternary ammonium salt, stir, a kind of interaction in quaternary ammonium salt and described benzene polycarboxylic acid's isomers, to form eutectic mixture solid;
(2) eutectic mixture solid step (1) being formed carries out filtering separation;
(3) the eutectic mixture solid after step (2) filtration is dried, to remove solvent residual in eutectic mixture;
(4) eutectic mixture after step (3) oven dry is mixed with counter solvent, stir, quaternary ammonium salt in eutectic mixture is dissolved in counter solvent, benzene polycarboxylic acid is solid, then filtering separation, obtains containing the counter solvent of quaternary ammonium salt and a kind of benzene polycarboxylic acid in described benzene polycarboxylic acid's isomer mixt;
(5) by the distillation of the counter solvent containing quaternary ammonium salt of step (4) gained, reclaim counter solvent, and obtain quaternary ammonium salt solid, realize the reclaiming of quaternary ammonium salt.
In aforesaid method, described benzene polycarboxylic acid's isomers is the mixture of phthalic acid and m-phthalic acid; Or the mixture of two or more in benzene-1, trimellitic acid and trimesic acid.
In aforesaid method, in step (1), the solvent of described dissolving benzene polycarboxylic acid isomer mixt is selected from one or more in butanone, acetone and pimelinketone, is preferably butanone.
In aforesaid method, in step (1), the mass concentration of described benzene polycarboxylic acid's isometry liquid solution is: phthalic acid is 0.5 ~ 3g/L, and benzene tricarboxylic acid is 0.1 ~ 10g/L.
In aforesaid method, in step (1), described quaternary ammonium salt is selected from one or more in choline chloride 60, tetramethyl ammonium chloride, etamon chloride and 4-propyl ammonium chloride, is preferably one or more in choline chloride 60, tetramethyl ammonium chloride and etamon chloride;
In aforesaid method, the total mass ratio of described quaternary ammonium salt and described benzene polycarboxylic acid's isomers is 0.1 ~ 2.1;
In aforesaid method, in step (1), whipping temp is 5
oc ~ 45
oC, be preferably 10
oc ~ 25
oc.
In aforesaid method, in step (1), churning time is 1 h ~ 5 h.
In aforesaid method, in step (4), described counter solvent is selected from one or more in Virahol, hexalin and n-propyl alcohol, is preferably Virahol.
In aforesaid method, in step (4), the mass ratio of the eutectic mixture after described counter solvent and described oven dry is 80 ~ 200.
In aforesaid method, in step (4), whipping temp is room temperature.
In aforesaid method, in step (4), churning time is 1 h ~ 5 h.
The principle of separation method of the present invention is: separated benzene polycarboxylic acid's isomers and the reactive force between quaternary ammonium salt are stronger than the reactive force between itself and solvent and other isomerss and quaternary amine or solvent, therefore, after adding quaternary ammonium salt, corresponding benzene polycarboxylic acid's isomers can be extracted from solvent, after reaching extraction equilibrium, continue to add quaternary amine, this benzene polycarboxylic acid's isomers can not continued extraction yet.
Compared with prior art, the separation method of benzene polycarboxylic acid's isomers of the present invention at least has following beneficial effect:
Compare with traditional post partition method, present method has many advantages, as greatly reduced the use of organic solvent for post is separated, has reduced energy consumption, has reduced environmental pollution; Present method is simple to operate in addition, and facility investment is few; Fractional dose greatly improves with respect to post separation, and efficiency is promoted.
Accompanying drawing explanation
The raffinate rate of phthalic acid and the relation between etamon chloride add-on in Fig. 1 solution
The raffinate rate of benzene tricarboxylic acid and the relation between etamon chloride add-on in Fig. 2 solution
Embodiment
Below in conjunction with embodiment, method of the present invention is described in further detail, but not thereby limiting the invention.
embodiment 1
The phthalic acid and the m-phthalic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with concentration and are respectively the phthalic acid of 1.1 g/L and 1.0 g/L and the butanone solution of m-phthalic acid mixture.Solution is placed in to 150 mL Erlenmeyer flasks.
In solution, add a small amount of etamon chloride, at room temperature magnetic agitation 2 h, then standing 15 min at every turn.Get 0.1 mL butanone solution and be diluted to 10 mL, with the phthalic acid in liquid-phase chromatographic analysis solution and the content of m-phthalic acid, repeat to add etamon chloride, until the content of the phthalic acid in solution no longer changes.The raffinate rate of phthalic acid in solution of take is ordinate zou, and the add-on of quaternary ammonium salt of take obtains Fig. 1 as X-coordinate mapping.
By this experimental result, can be determined the add-on of quaternary ammonium salt, and then be used for separation of benzene dioctyl phthalate isomers.As seen from the figure, in the extraction of phthalic acid, reach after balance, even if add quaternary ammonium salt, phthalic acid can not separated out yet again again.The deficiency that the amount of quaternary ammonium salt adds from experiment, can obtain quaternary ammonium salt and the total mass ratio of phthalic acid is 3.2, if can not reach separating effect.If it is too much that the amount of quaternary ammonium salt adds, can cause waste, increase the weight of separation costs.
embodiment 2
The benzene-1, trimellitic acid and the trimesic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with the butanone solution of benzene-1, trimellitic acid and trimesic acid mixture that concentration is respectively 3.0 g/L, 3.1 g/L and 3.4 g/L.Solution is placed in to 150 mL Erlenmeyer flasks.
In solution, add a small amount of etamon chloride, at room temperature magnetic agitation 2 h, then standing 15 min at every turn.Get 0.1 mL butanone solution and be diluted to 10 mL, the content with the benzene tricarboxylic acid in liquid-phase chromatographic analysis solution, repeats to add etamon chloride, until the content of the benzene front three carboxylic acid in solution no longer changes.The raffinate rate of benzene tricarboxylic acid in solution of take is ordinate zou, and the add-on of quaternary ammonium salt of take obtains Fig. 2 as X-coordinate mapping.
By this experimental result, can be determined the add-on of quaternary ammonium salt, to be used for separation of benzene tricarboxylic acid isomers.As seen from the figure, in the extraction of trimellitic acid, reach after balance, even if add quaternary ammonium salt, trimellitic acid can not separated out yet again again.The deficiency that the amount of quaternary ammonium salt adds from experiment, can obtain quaternary ammonium salt and the total mass ratio of benzene tricarboxylic acid is 1.6, if can not reach separating effect.If it is too much that the amount of quaternary ammonium salt adds, can cause waste, increase the weight of separation costs.
embodiment 3
The phthalic acid and the m-phthalic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with concentration and are respectively the phthalic acid of 1.1 g/L and 1.0 g/L and the butanone solution of m-phthalic acid mixture.Solution is placed in to 150 mL Erlenmeyer flasks.
(1) in Erlenmeyer flask, add 0.26 g etamon chloride, at room temperature magnetic agitation 2 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, content with the phthalic acid in liquid-phase chromatographic analysis solution and m-phthalic acid, known by analysis, 59.3% phthalic acid elder generation and etamon chloride form eutectic mixture and separate out, and the content of m-phthalic acid remains unchanged.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 40 g Virahols, at room temperature magnetic agitation 1 h.Then filter, obtain aqueous isopropanol and phthalic acid solid containing etamon chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain etamon chloride solid, thereby realize the reclaiming of etamon chloride.
(2) in above-mentioned filtrate, add again 0.41 g etamon chloride, at room temperature magnetic agitation 3 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the phthalic acid in liquid-phase chromatographic analysis solution and the content of m-phthalic acid.Known by analysis, 100% m-phthalic acid and etamon chloride form eutectic and separate out.In solution, remain 41.7% phthalic acid.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 50 g Virahols, at room temperature magnetic agitation 1 h.Then filter, obtain aqueous isopropanol and m-phthalic acid solid containing etamon chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain etamon chloride solid, thereby realize the reclaiming of etamon chloride.
embodiment 4
The benzene-1 and the trimellitic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with concentration and are respectively the benzene-1 of 3.8 g/L and 3.3 g/L and the butanone solution of trimellitic acid mixture.Solution is placed in to 150 mL Erlenmeyer flasks.
In Erlenmeyer flask, add 0.75 g choline chloride 60, at room temperature magnetic agitation 4 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1 and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, choline chloride 60 can be separated 79.2% benzene-1 from butanone solution, but trimellitic acid is still stayed in butanone solution.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 150 g Virahols, at room temperature magnetic agitation 5 h.Then filter, obtain aqueous isopropanol and the benzene-1 solid of chloride containing choline.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain choline chloride 60 solid, thereby realize the reclaiming of choline chloride 60.
embodiment 5
The trimellitic acid and the trimesic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with concentration and are respectively the trimellitic acid of 3.2 g/L and 3.5g/L and the butanone solution of trimesic acid mixture.Solution is placed in to 150 mL Erlenmeyer flasks.
In Erlenmeyer flask, add 0.76 g choline chloride 60.At room temperature magnetic agitation 4 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of trimellitic acid and trimesic acid in liquid-phase chromatographic analysis solution.Known by analysis, choline chloride 60 can be separated 69.6% trimesic acid from butanone solution, but trimellitic acid is still stayed in butanone solution.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
odry 5 h in C baking oven, remove the butanone in the mixed solid compound of eutectic.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 150 g Virahols, at room temperature magnetic agitation 5 h.Then filter, obtain containing choline chloride 60 aqueous isopropanol and trimesic acid solid.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain choline chloride 60 solid, thereby realize the reclaiming of choline chloride 60.
embodiment 6
The benzene-1 and the trimesic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with concentration and are respectively the benzene-1 of 3.1 g/L and 3.2 g/L and the butanone solution of trimesic acid mixture.Solution is placed in to 150 mL Erlenmeyer flasks.
(1) in Erlenmeyer flask, add 0.18 g tetramethyl ammonium chloride.At room temperature magnetic agitation 3 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1 and trimesic acid in liquid-phase chromatographic analysis solution.Known by analysis, 55.9% benzene-1 and tetramethyl ammonium chloride form eutectic and separate out, and the content of trimesic acid remains unchanged.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 50 g Virahols, at room temperature magnetic agitation 3 h.Then filter, obtain aqueous isopropanol and benzene-1 containing tetramethyl ammonium chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain tetramethyl ammonium chloride solid, thereby realize the reclaiming of tetramethyl ammonium chloride.
(2) in above-mentioned filtrate, add 0.26 g tetramethyl ammonium chloride, at room temperature magnetic agitation 3 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1 and trimesic acid in liquid-phase chromatographic analysis solution.Known by analysis, 100% trimesic acid and 45.1% benzene-1 and tetramethyl ammonium chloride form eutectic and separate out.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 60 g Virahols, at room temperature magnetic agitation 3 h.Then filter, obtain containing tetramethyl ammonium chloride aqueous isopropanol and benzene polycarboxylic acid's solid.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain tetramethyl ammonium chloride solid, thereby realize the reclaiming of tetramethyl ammonium chloride.
embodiment 7
The benzene-1 and the trimellitic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with concentration and are respectively the benzene-1 of 3.2 g/L and 3.0 g/L and the butanone solution of trimellitic acid mixture.Solution is placed in to 150 mL Erlenmeyer flasks.
(1) in Erlenmeyer flask, add 0.36 g tetramethyl ammonium chloride.At room temperature magnetic agitation 3 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1 and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 91.2% benzene-1 and tetramethyl ammonium chloride form eutectic and separate out, and the content of trimellitic acid remains unchanged.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 70 g Virahols, at room temperature magnetic agitation 3 h.Then filter, obtain aqueous isopropanol and benzene-1 containing tetramethyl ammonium chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain tetramethyl ammonium chloride solid, thereby realize the reclaiming of tetramethyl ammonium chloride.
(2) in above-mentioned filtrate, add 0.41 g tetramethyl ammonium chloride, at room temperature magnetic agitation 3 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1 and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 87.9% trimellitic acid, 8.8% benzene-1 start to form eutectic with tetramethyl ammonium chloride and separate out.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 80 g Virahols, at room temperature magnetic agitation 3 h.Then filter, obtain the aqueous isopropanol and the benzene polycarboxylic acid's solid that contain tetramethyl ammonium chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain tetramethyl ammonium chloride solid, thereby realize the reclaiming of tetramethyl ammonium chloride.
embodiment 8
The trimellitic acid and the trimesic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with concentration at the trimellitic acid of 3.2 g/L and 3.5 g/L and the butanone solution of trimesic acid mixture.Solution is placed in to 150 mL Erlenmeyer flasks.
(1) in Erlenmeyer flask, add 0.25 g tetramethyl ammonium chloride.At room temperature magnetic agitation 3 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of trimesic acid and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 95.1% trimesic acid elder generation and tetramethyl ammonium chloride form eutectic and separate out, and the content of trimellitic acid remains unchanged.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 60 g Virahols, at room temperature magnetic agitation 3 h.Then filter, obtain aqueous isopropanol and trimesic acid containing tetramethyl ammonium chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain tetramethyl ammonium chloride solid, thereby realize the reclaiming of tetramethyl ammonium chloride.
(2) in above-mentioned filtrate, add 0.45 g tetramethyl ammonium chloride, at room temperature magnetic agitation 3 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of trimesic acid and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 87.9% trimellitic acid, 4.9% trimesic acid start to form eutectic with tetramethyl ammonium chloride and separate out.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 80 g Virahols, at room temperature magnetic agitation 3 h.Then filter, obtain aqueous isopropanol and benzene polycarboxylic acid's solid.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain tetramethyl ammonium chloride solid, thereby realize the reclaiming of tetramethyl ammonium chloride.
embodiment 9
The benzene-1 and the trimesic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with concentration and are respectively the benzene-1 of 3.3 g/L and 3.4 g/L and the butanone solution of trimesic acid mixture.Solution is placed in to 150 mL Erlenmeyer flasks.
(1) in Erlenmeyer flask, add 0.49 g etamon chloride.At room temperature magnetic agitation 2 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1 and trimesic acid in liquid-phase chromatographic analysis solution.Known by analysis, 86.0% benzene-1 and etamon chloride form eutectic and separate out, and the content of trimesic acid remains unchanged.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 80 g Virahols, at room temperature magnetic agitation 1 h.Then filter, obtain aqueous isopropanol and benzene-1 containing etamon chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain etamon chloride solid, thereby realize the reclaiming of etamon chloride.
(2) in above-mentioned filtrate, add 0.41 g tetramethyl ammonium chloride, at room temperature magnetic agitation 2 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1 and trimesic acid in liquid-phase chromatographic analysis solution.Known by analysis, 100% trimesic acid and 14.0% benzene-1 start to form eutectic with etamon chloride and separate out.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 80 g Virahols, at room temperature magnetic agitation 1 h.Then filter, obtain aqueous isopropanol and benzene polycarboxylic acid's solid.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain etamon chloride solid, thereby realize the reclaiming of etamon chloride.
embodiment 10
The benzene-1 and the trimellitic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with concentration respectively at the benzene-1 of 3.1 g/L and 3.5 g/L and the butanone solution of trimellitic acid mixture.Solution is placed in to 150 mL Erlenmeyer flasks.
(1) in Erlenmeyer flask, add 0.52 g etamon chloride.At room temperature magnetic agitation 2 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1 and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 100% benzene-1 and etamon chloride form eutectic and separate out, and the content of trimellitic acid remains unchanged.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 100 g Virahols, at room temperature magnetic agitation 1 h.Then filter, obtain aqueous isopropanol and benzene-1 containing etamon chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain etamon chloride solid, thereby realize the reclaiming of etamon chloride.
(2) in above-mentioned filtrate, add 0.53 g etamon chloride, at room temperature magnetic agitation 2 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1 and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 100% trimellitic acid and etamon chloride form eutectic and separate out.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 100 g Virahols, at room temperature magnetic agitation 1 h.Then filter, obtain the aqueous isopropanol and the benzene polycarboxylic acid's solid that contain etamon chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain etamon chloride solid, thereby realize the reclaiming of etamon chloride.
embodiment 11
The trimellitic acid and the trimesic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with concentration and are respectively the trimellitic acid of 3.1 g/L and 3.4 g/L and the butanone solution of trimesic acid mixture.Solution is placed in to 150 mL Erlenmeyer flasks.
(1) in Erlenmeyer flask, add 0.51 g etamon chloride.At room temperature magnetic agitation 2 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of trimesic acid and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 85.0% trimesic acid and etamon chloride form eutectic and separate out, and the content of trimellitic acid remains unchanged.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 110 g Virahols, at room temperature magnetic agitation 1 h.Then filter, obtain aqueous isopropanol and trimesic acid containing etamon chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain etamon chloride solid, thereby realize the reclaiming of etamon chloride.
(2) in above-mentioned filtrate, add 0.54 g etamon chloride, at room temperature magnetic agitation 2 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of trimesic acid and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 91.3% trimellitic acid and 15.0% trimesic acid start to form eutectic with etamon chloride and separate out.Therefore, etamon chloride can be separated most of trimesic acid and trimellitic acid.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 110 g Virahols, at room temperature magnetic agitation 1 h.Then filter, obtain the aqueous isopropanol and the benzene polycarboxylic acid's solid that contain etamon chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain etamon chloride solid, thereby realize the reclaiming of etamon chloride.
embodiment 12
The benzene-1, trimellitic acid and the trimesic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with the butanone solution of benzene-1, trimellitic acid and trimesic acid mixture that concentration is respectively 3.0 g/L, 3.1 g/L and 3.4 g/L.Solution is placed in to 150 mL Erlenmeyer flasks.
In Erlenmeyer flask, add 1.5 g choline chloride 60s.At room temperature magnetic agitation 4 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1, trimesic acid and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, choline chloride 60 can be separated the trimesic acid of 79.2% benzene-1 and 69.6% simultaneously simultaneously from butanone solution, but trimellitic acid is still stayed in butanone solution.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 300 g Virahols, at room temperature magnetic agitation 5 h.Then filter, obtain the aqueous isopropanol and the benzene polycarboxylic acid's solid that contain choline chloride 60.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain choline chloride 60 solid, thereby realize the reclaiming of choline chloride 60.
embodiment 13
The benzene-1, trimellitic acid and the trimesic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with the butanone solution of benzene-1, trimellitic acid and trimesic acid mixture that concentration is respectively 3.0 g/L, 3.1 g/L and 3.4 g/L.Solution is placed in to 150 mL Erlenmeyer flasks.
(1) in Erlenmeyer flask, add 0.18 g tetramethyl ammonium chloride.At room temperature magnetic agitation 3 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1, trimesic acid and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 55.9% benzene-1 and tetramethyl ammonium chloride form eutectic and separate out, and the content of trimellitic acid and trimesic acid remains unchanged.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 80 g Virahols, at room temperature magnetic agitation 3 h.Then filter, obtain the aqueous isopropanol and the benzene polycarboxylic acid's solid that contain tetramethyl ammonium chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain tetramethyl ammonium chloride solid, thereby realize the reclaiming of tetramethyl ammonium chloride.
(2) in above-mentioned filtrate, add 0.26 g tetramethyl ammonium chloride.At room temperature magnetic agitation 3 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1, trimesic acid and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 87.2% trimesic acid and 28.9% benzene-1 and tetramethyl ammonium chloride form eutectic and separate out.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 100 g Virahols, at room temperature magnetic agitation 3 h.Then filter, obtain the aqueous isopropanol and the benzene polycarboxylic acid's solid that contain tetramethyl ammonium chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain tetramethyl ammonium chloride solid, thereby realize the reclaiming of tetramethyl ammonium chloride.
(3) in above-mentioned filtrate, add 0.56 g tetramethyl ammonium chloride.At room temperature magnetic agitation 3 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1, trimesic acid and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 87.9% trimellitic acid, 8.8% benzene-1 and 4.9% trimesic acid start to form eutectic with tetramethyl ammonium chloride and separate out.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 150 g Virahols, at room temperature magnetic agitation 3 h.Then filter, obtain the aqueous isopropanol and the benzene polycarboxylic acid's solid that contain tetramethyl ammonium chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain tetramethyl ammonium chloride solid, thereby realize the reclaiming of tetramethyl ammonium chloride.
embodiment 14
The benzene-1, trimellitic acid and the trimesic acid mixture that take certain mass are dissolved in 100 mL butanone, are mixed with the butanone solution of benzene-1, trimellitic acid and trimesic acid mixture that concentration is respectively 3.0 g/L, 3.1 g/L and 3.4 g/L.Solution is placed in to 150 mL Erlenmeyer flasks.
(1) in Erlenmeyer flask, add 0.51 g etamon chloride.At room temperature magnetic agitation 2 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1, trimesic acid and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 86.0% benzene-1 and etamon chloride form eutectic and separate out, and the content of trimesic acid and trimellitic acid remains unchanged.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 100 g Virahols, at room temperature magnetic agitation 1 h.Then filter, obtain aqueous isopropanol and benzene-1 containing etamon chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain etamon chloride solid, thereby realize the reclaiming of etamon chloride.
(2) in above-mentioned filtrate, add 0.46 g etamon chloride, at room temperature magnetic agitation 2 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1, trimellitic acid and trimesic acid in liquid-phase chromatographic analysis solution.Known by analysis, 85.0% trimesic acid and 14.0% benzene-1 and etamon chloride form eutectic and separate out.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 80 g Virahols, at room temperature magnetic agitation 1 h.Then filter, obtain the aqueous isopropanol and the benzene polycarboxylic acid's solid that contain etamon chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain etamon chloride solid, thereby realize the reclaiming of etamon chloride.
(3) in above-mentioned filtrate, add 0.54 g etamon chloride, at room temperature magnetic agitation 2 h, then standing 15 min.Get 0.1 mL butanone solution and be diluted to 10 mL, with the content of benzene-1, trimesic acid and trimellitic acid in liquid-phase chromatographic analysis solution.Known by analysis, 91.3% trimellitic acid and 1.0% trimesic acid start to form eutectic with etamon chloride and separate out.Solution filter is obtained to butanone filtrate and eutectic solid mixture.By eutectic solid mixture 60
oin C baking oven, dry 5 h, remove the butanone in eutectic solid mixture.Dried eutectic solid mixture is placed in to 250 mL Erlenmeyer flasks.Add 100 g Virahols, at room temperature magnetic agitation 1 h.Then filter, obtain the aqueous isopropanol and the benzene polycarboxylic acid's solid that contain etamon chloride.By aqueous isopropanol evaporate to dryness, reclaim counter solvent Virahol, and obtain etamon chloride solid, thereby realize the reclaiming of etamon chloride.
Claims (9)
1. a separation method for benzene polycarboxylic acid's isomers, the method comprises the steps:
(1) in the solution of benzene polycarboxylic acid's isomers, add quaternary ammonium salt, stir, make a kind of interaction in quaternary ammonium salt and described benzene polycarboxylic acid's isomers, to form eutectic mixture;
(2) eutectic mixture step (1) being formed filters;
(3) eutectic mixture after step (2) filtration is dried, to remove solvent residual in eutectic mixture;
(4) eutectic mixture after step (3) is dried mixes with counter solvent, stirs, and filtration, obtains containing a kind of in the counter solvent of quaternary ammonium salt and described benzene polycarboxylic acid's isomers;
(5) counter solvent containing quaternary ammonium salt step (4) being obtained distills, and reclaims counter solvent, and obtains quaternary ammonium salt solid.
2. separation method according to claim 1, is characterized in that, described benzene polycarboxylic acid's isomers is the mixture of phthalic acid and m-phthalic acid; Or the mixture of two or more in benzene-1, trimellitic acid and trimesic acid.
3. according to the separation method described in claim 1, it is characterized in that, in step (1), the solvent that described benzene polycarboxylic acid's isometry liquid solution is used is selected from one or more in butanone, acetone and pimelinketone, is preferably butanone.
4. according to the separation method described in any one in claims 1 to 3, it is characterized in that, in step (1), the mass concentration of described benzene polycarboxylic acid's isometry liquid solution is: benzene dicarboxylic acid is 0.5 ~ 3g/L, and benzene tricarbonic acid is 0.1 ~ 10g/L.
5. according to the separation method described in any one in claim 1 to 4, it is characterized in that, in step (1), described quaternary ammonium salt is selected from one or more in choline chloride 60, tetramethyl ammonium chloride, etamon chloride and 4-propyl ammonium chloride, is preferably one or more in choline chloride 60, tetramethyl ammonium chloride and etamon chloride.
6. according to the separation method described in any one in claim 1 to 5, it is characterized in that, in aforesaid method, the mass ratio of described quaternary ammonium salt and described benzene polycarboxylic acid's isomers is 0.1 ~ 2.1.
7. according to the separation method described in any one in claim 1 to 6, it is characterized in that, in aforesaid method, in step (1), whipping temp is 5
oc ~ 45
oC, be preferably 10
oc ~ 25
oc; Churning time is 1 h ~ 5 h.
8. according to the separation method described in claim 1, it is characterized in that, in step (4), described counter solvent is selected from one or more in Virahol, hexalin and n-propyl alcohol, is preferably Virahol.
9. according to the separation method described in claim 1, it is characterized in that, in step (4), the mass ratio of the eutectic mixture after described counter solvent and described oven dry is 80 ~ 200, under room temperature, stirs, and churning time is 1 h ~ 5 h.
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| CN107286014A (en) * | 2016-04-12 | 2017-10-24 | 北京化工大学 | A kind of separation method of Pyromellitic Acid and trimellitic acid mixture |
| CN110180329A (en) * | 2019-06-25 | 2019-08-30 | 中国石油大学(华东) | Novel benzene series volatile organic compounds absorbent and its preparation method and application |
| CN111359258A (en) * | 2020-03-06 | 2020-07-03 | 哈尔滨工业大学（威海） | Novel system for separating and purifying hydrophobic eutectic solvent of weak protonic acid and method for purifying weak protonic acid |
| CN113200869A (en) * | 2021-04-28 | 2021-08-03 | 南京长江江宇环保科技有限公司 | Method for recovering tetramethylammonium chloride from semiconductor development wastewater |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107286014A (en) * | 2016-04-12 | 2017-10-24 | 北京化工大学 | A kind of separation method of Pyromellitic Acid and trimellitic acid mixture |
| CN107286014B (en) * | 2016-04-12 | 2020-09-22 | 北京化工大学 | Separation method of mixture of pyromellitic acid and trimellitic acid |
| CN110180329A (en) * | 2019-06-25 | 2019-08-30 | 中国石油大学(华东) | Novel benzene series volatile organic compounds absorbent and its preparation method and application |
| CN110180329B (en) * | 2019-06-25 | 2022-02-25 | 中国石油大学(华东) | Novel benzene series volatile organic compound absorbent, preparation method and application thereof |
| CN111359258A (en) * | 2020-03-06 | 2020-07-03 | 哈尔滨工业大学（威海） | Novel system for separating and purifying hydrophobic eutectic solvent of weak protonic acid and method for purifying weak protonic acid |
| CN111359258B (en) * | 2020-03-06 | 2021-11-23 | 哈尔滨工业大学（威海） | Novel system for separating and purifying hydrophobic eutectic solvent of weak protonic acid and method for purifying weak protonic acid |
| CN113200869A (en) * | 2021-04-28 | 2021-08-03 | 南京长江江宇环保科技有限公司 | Method for recovering tetramethylammonium chloride from semiconductor development wastewater |
| CN113200869B (en) * | 2021-04-28 | 2023-06-23 | 南京长江江宇环保科技股份有限公司 | Method for recycling tetramethyl ammonium chloride from semiconductor development wastewater |
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