CN100546971C - A kind of separation method of nitro phthalandione isomer mixture - Google Patents
A kind of separation method of nitro phthalandione isomer mixture Download PDFInfo
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Abstract
A kind of separation method of nitro phthalandione isomer mixture, belong to the fine chemical technology field, under the heating condition, with nitro phthalandione isomer mixture dissolving fully in solvent, decrease temperature crystalline is isolated crystalline 4-nitrophthalic acid crude product then; Filtrate behind the separation 4-nitrophthalic acid crude product is carried out evaporative crystallization, and solid phase is a 3-nitrophthalic acid crude product; Described solvent is 1,4-dioxane or its homologue at least any one.Technical process weak point of the present invention, less investment, production cost are low, quality product, shaping well, big, the flexible operation of production intensity, production process is safe and reliable and characteristics such as process three-waste free discharge, can significantly reduce the comprehensive production cost of 4-nitrophthalic acid product.
Description
Technical field
The invention belongs to the fine chemical technology field, specifically, the Crystallization Separation method that relates to a kind of nitro phthalandione isomer mixture, particularly a kind of being used for by the nitrated 3-nitrophthalic acid that obtains of phthalic anhydride and 4-nitro phthalandione isomer mixture or by the Crystallization Separation method of the by product of the nitrated production of phthalic anhydride 3-nitrophthalic acid.
Background technology
3-nitrophthalic acid and 4-nitrophthalic acid are isomerss, and molecular formula is respectively:
3-nitrophthalic acid 4-nitrophthalic acid
3-nitrophthalic acid (CAS Registry No.603-11-2), another name 3-nitro-1,2-benzenedicarboxylic acid, 3-nitrophthalic acid, m-nitro dioctyl phthalate, outward appearance is white to the off-white color crystalline powder, not flammable, torpescence, very stable generally speaking, fusing point is 210-216 ℃.Water soluble, alcohols are dissolved in ether slightly, are the important intermediate of agricultural chemicals, pigment, dyestuff, plastics, electron trade.
4-nitrophthalic acid (CAS Registry No.610-27-5), outward appearance is off-white color or pale yellow powder, and fusing point is 164～168 ℃, and solubleness is bigger in water, is insoluble to benzene, tetracol phenixin and dithiocarbonic anhydride.Not only be used for dyestuff, paint, macromolecular material, agricultural chemicals aspect, but also be applied in pharmaceutically to produce antitumor drug.
When preparation 3-nitrophthalic acid, the 4-nitrophthalic acid generates simultaneously.Because the solubleness of 4-nitrophthalic acid in the aqueous solution is bigger, the 3-nitrophthalic acid is in the aqueous solution after the Crystallization Separation, still contain a large amount of 4-nitrophthalic acids and a spot of 3-nitrophthalic acid in the mother liquor, this mixture utility value is lower, suitable partially as the by product price, all send as waste residue generally speaking and burn the station burning disposal, both contaminate environment caused the waste of resource again.If its separation can be obtained 3-nitrophthalic acid and 4-nitrophthalic acid product, added value increases substantially, and purposes is very extensive.
In the document to having done 3-nitrophthalic acid and separating of 4-nitro phthalandione isomer mixture a large amount of work.U.S. Pat 4284797 discloses a kind of 3-of utilization nitrophthalic acid and the dissolubility difference of 4-nitrophthalic acid salt in solution, at first adjust 3-nitrophthalic acid and 4-nitrophthalic acid pH value of aqueous solution with alkali, change it into corresponding salt, utilize acid to change it into 4-nitrophthalic acid after the filtration again, thereby realize separating of 3-nitrophthalic acid and 4-nitrophthalic acid.
Chinese patent CN1651399 has set forth a kind of preparation technology who utilizes the by product purified 4-nitro phthalic acid of producing the 3-nitrophthalic acid.Utilize to produce byproduct content that 3-nitrophthalic acid product produces less than the 4-nitrophthalic acid of 80% (wt) and alcohol under 0-130 ℃, carrying out esterification under the catalyst action, obtain content greater than 99% 4-nitrophthalic acid dialkyl, then 4-nitrophthalic acid dialkyl and alkali are carried out saponification reaction in solvent under 0～120 ℃, obtain content greater than 99% 4-nitrophthalic acid.
Chinese patent CN1740138 discloses a kind of method for preparing the 4-nitrophthalic acid from the reaction solution of the nitrated preparation of phthalic anhydride 3-nitrophthalic acid.At first cold filtration is gone the reaction mother liquor of 3-nitrophthalic acid under agitation to be added in the cold water of 1.5-3.5 times of volume, cool overnight, filter out the thick product of 4-nitrophthalic acid, the water that then the thick product of 4-nitrophthalic acid that obtains is added 2.5-3.5 times of quality is stirred to the nitric acid that dissolving fully adds afterwards the 0.08-0.12 volume of this liquor capacity at normal temperatures, with ether extraction 4-nitrophthalic acid, get ether extracted liquid; Again ether extracted liquid is boiled off ether, pour out debris while hot, crystallisation by cooling promptly gets 4-nitrophthalic acid product.
Although above-mentioned several method can be realized separating of 3-nitrophthalic acid and 4-nitrophthalic acid mixture, obtain highly purified 3-nitrophthalic acid and 4-nitrophthalic acid product, but Production Flow Chart is longer, cost is very high, there is serious three waste discharge problem simultaneously, causes the market value of 4-nitrophthalic acid more much higher than 3-nitrophthalic acid.Therefore how to realize effective separation of 3-nitrophthalic acid and 4-nitrophthalic acid mixture, shortened process, reduce production costs, reduce or eliminate the discharging of the three wastes, become the problem that present urgent need solves, for the production of 4-nitrophthalic acid and apply and have important practical significance.
Summary of the invention
Purpose of the present invention is exactly in order to overcome the deficiency of existing 3-nitrophthalic acid and the sepn process of 4-nitro phthalandione isomer mixture, and a kind of technical process is short, the separation method of the nitro phthalandione isomer mixture of being convenient to operate, reduce production costs, reduce or eliminate three waste discharge and provide.
Technical scheme of the present invention is: under the heating condition, with nitro phthalandione isomer mixture dissolving fully in solvent, decrease temperature crystalline is isolated crystalline 4-nitrophthalic acid crude product then; Filtrate behind the separation 4-nitrophthalic acid crude product is carried out evaporative crystallization, and solid phase is a 3-nitrophthalic acid crude product; Described solvent comprises 1,4-dioxane or its homologue at least any one.
The present invention compares with the separating technology of present nitro phthalandione isomer, this crystallization processes flow process weak point, less investment, production cost are low, quality product, shaping well, big, the flexible operation of production intensity, production process is safe and reliable and characteristics such as process three-waste free discharge, can significantly reduce the comprehensive production cost of 4-nitrophthalic acid product.The present invention is that raw material carries out Crystallization Separation and obtains highly purified 3-nitrophthalic acid and 4-nitrophthalic acid product with the nitro phthalandione isomer mixture, also for the nitrated preparation of phthalic anhydride 4-nitrophthalic acid product provides a new approach, the comprehensive utilization of producing the by product of 3-nitrophthalic acid simultaneously for phthalic anhydride is nitrated provides new thinking.
Separate object of the present invention---nitro phthalandione isomer mainly contains 3-nitrophthalic acid, 4-nitrophthalic acid and a spot of impurity, also can contain water, behind the employing such scheme, has the following advantages:
(1) technical process is shortened, and the process cost of product reduces;
(2) the crystallization operation temperature is low, and is little to the equipment corrosion degree, the security of crystallization operation, good reliability;
(3) improve operating environment, reduce three waste discharge and environmental pollution.
The method that the present invention obtains the higher 4-nitrophthalic acid of purity is: 1, the recrystallization separation and purification obtains the 4-nitrophthalic acid in the 4-dioxane with 4-nitrophthalic acid crude product.
The method that the present invention obtains the higher 3-nitrophthalic acid of purity is: 3-nitrophthalic acid crude product is dissolved the post crystallization separation obtain the 3-nitrophthalic acid in water.
Concrete steps are as follows:
A, in the stirring and dissolving still, add nitro phthalandione isomer mixture and solvent, be warming up to nitro phthalandione isomer mixture and dissolve fully, then decrease temperature crystalline;
B, the solidliquid mixture of a step gained is filtered, filtrate enters vaporizer, and filter cake is a 4-nitrophthalic acid crude product;
C, 4-nitrophthalic acid crude product is added 4-nitrophthalic acid recrystallizer, add solvent again, be warming up to dissolving fully, decrease temperature crystalline filters then, and the filter cake drying gets the 4-nitrophthalic acid;
D, in vaporizer the filtrate of b step is evaporated, solid phase is a 3-nitrophthalic acid crude product, and 3-nitrophthalic acid crude product is placed 3-nitrophthalic acid crystallizer;
E, in 3-nitrophthalic acid crystallizer, add entry, be warming up to fully dissolving, decrease temperature crystalline filters then, gets the crystalline filter cake, drying gets the 3-nitrophthalic acid again.
In addition, for reducing discharging, improving the rate of recovery, the present invention is also evaporated the filtrate of e in vaporizer, turns back to behind the water condensation in the 3-nitrophthalic acid crystallizer, and solid phase turns back to stirring and dissolving equipment.
Service temperature is that the freezing point of system is between the reflux temperature of solvent in the above-mentioned Crystallization Separation process of the present invention.
Embodiment
With the nitro phthalandione isomer mixture is raw material, produces the crystallization separation process step of 3-nitrophthalic acid and 4-nitrophthalic acid:
Material preparation:
1, nitro phthalandione isomer: mainly contain 3-nitrophthalic acid, 4-nitrophthalic acid and a spot of impurity, also can contain water.
2, solvent: contain 1 at least, 4-dioxane or its homologue at least any one.Can be 1,4-dioxane, or its homologue, or 1, the mixture of 4-dioxane and homologue thereof and other solvents.
Solvent 1:1, the 4-dioxane.
Solvent 2:1, the 3-dioxolane
Solvent 3:1,4-dioxane and 1, the mixture of 3-dioxolane, its volume ratio is 6: 5
Solvent 4:1, the mixture of 4-dioxane and water, its volume ratio is 8: 2.
Solvent 5:1, the mixture of 3-dioxolane and acetone, its volume ratio is 7: 3
Solvent 6:1,4-dioxane and alcoholic acid mixture, its volume ratio is 8: 2.
Embodiment one:
In this example, the mass ratio of 3-nitrophthalic acid and 4-nitrophthalic acid is 3: 7 in the nitro phthalandione isomer mixture.
In the stirring and dissolving still, add nitro phthalandione isomer mixture 100g and 100ml solvent 1:1, the 4-dioxane, heating is warming up to 65 ℃ mixture is all dissolved while stirring, system temperature is reduced to 0 ℃, crystallization 2h under agitation condition.The crystallization of 4-nitrophthalic acid is separated out, and filters, and filter cake 60g is a 4-nitrophthalic acid crude product, and the purity of 4-nitrophthalic acid is 93.5%, and filtrate A enters vaporizer.
60g filter cake 4-nitrophthalic acid crude product is entered 4-nitrophthalic acid recrystallizer, add 1 simultaneously, 4-dioxane 50ml, heating while stirring, treat whole dissolvings, system temperature is reduced to 0 ℃, crystallization 2h under agitation condition, filter, filtration cakes torrefaction gets the 4-nitrophthalic acid product 32g of content 99.2% (wt).
In vaporizer filtrate A is evaporated, solvent 1:1,4-dioxane turn back in the stirring and dissolving still, and solid phase is the crude product 25g that is rich in the 3-nitrophthalic acid.
The crude product that will be rich in the 3-nitrophthalic acid again places 3-nitrophthalic acid crystallizer, add 300g water simultaneously, be warming up to dissolving fully, cool off system temperature then and reduce to 0 ℃ of post crystallization, after the filtration, the filter cake drying gets the 3-nitrophthalic acid product 18g of purity 99.2%; Liquid phase enters in the vaporizer evaporates, and turns back to behind the water condensation in the 3-nitrophthalic acid crystallizer, and solid phase turns back to the stirring and dissolving still.
Embodiment two:
In this example, the mass ratio of 3-nitrophthalic acid and 4-nitrophthalic acid is 2: 8 in the nitro phthalandione isomer mixture.
In the stirring and dissolving still, add nitro phthalandione isomer mixture 100g and 100ml solvent 2:1, the 3-dioxolane, heating is warming up to 71 ℃ mixture is all dissolved while stirring, system temperature is reduced to 5 ℃ then, stirred crystallization 2h.The crystallization of 4-nitrophthalic acid is separated out, and filters, and filter cake 59g is a 4-nitrophthalic acid crude product, and the purity of 4-nitrophthalic acid is 92.1%, and liquor B enters vaporizer.
The 59g filter cake is entered 4-nitrophthalic acid recrystallizer, add 1 simultaneously, 4-dioxane 50ml, heating while stirring, treat whole dissolvings, system temperature is reduced to 5 ℃ then, crystallization 2h under agitation condition, filter, filtration cakes torrefaction gets the 4-nitrophthalic acid elaboration 26g of content 99.3% (wt).
In vaporizer liquor B is evaporated, solvent 2:1,3-dioxolane turn back in the stirring and dissolving still, and solid phase is the crude product 16g that is rich in the 3-nitrophthalic acid.
The crude product that will be rich in the 3-nitrophthalic acid again enters 3-nitrophthalic acid crystallizer, add 100g water simultaneously, be warming up to dissolving fully, cool off system temperature then and reduce to 0 ℃ of post crystallization, after the filtration, the filter cake drying gets the 3-nitrophthalic acid product 13g of purity 99.3%; Liquid phase enters in the vaporizer evaporates, and turns back to behind the water condensation in the 3-nitrophthalic acid crystallizer, and solid phase turns back to the stirring and dissolving still.
Embodiment three:
In this example, the mass ratio of 3-nitrophthalic acid and 4-nitrophthalic acid is 3: 7 in the nitro phthalandione isomer mixture.
In the stirring and dissolving still, add nitro phthalandione isomer mixture 100g and 100ml solvent 3:1,4-dioxane and 1, the mixture of 3-dioxolane, its volume ratio is 6: 5, and heating is warming up to 70 ℃ mixture is all dissolved while stirring, system temperature is reduced to 5 ℃ then, stirred crystallization 2h.The crystallization of 4-nitrophthalic acid is separated out, and filters, and filter cake 54g is a 4-nitrophthalic acid crude product, and the purity of 4-nitrophthalic acid is 93.0%, and liquor C enters vaporizer.
The 54g filter cake enters 4-nitrophthalic acid recrystallizer, add solvent 1 simultaneously, 4-dioxane 50ml, heating while stirring, after treating all dissolvings, system temperature is reduced to 0 ℃, crystallization 2h under agitation condition, filter, filtration cakes torrefaction gets the 4-nitrophthalic acid elaboration 27g of content 99.1% (wt).
In vaporizer, liquor C is evaporated, solvent 3:1,4-dioxane and 1, the mixture of 3-dioxolane turn back in the stirring and dissolving still, and solid phase is the crude product 22g that is rich in the 3-nitrophthalic acid.
The crude product that is rich in the 3-nitrophthalic acid enters 3-nitrophthalic acid crystallizer, add 300g water simultaneously, be warming up to dissolving fully, cool off system temperature then and reduce to 0 ℃ of post crystallization, after the filtration, the filter cake drying gets the 3-nitrophthalic acid product 16g of purity 99.2%; Liquid phase enters in the vaporizer evaporates, and turns back to behind the water condensation in the 3-nitrophthalic acid crystallizer, and solid phase turns back to the stirring and dissolving still.
Embodiment four:
In this example, the mass ratio of 3-nitrophthalic acid and 4-nitrophthalic acid is 3: 7 in the nitro phthalandione isomer mixture.
In the stirring and dissolving still, add nitro phthalandione isomer mixture 100g and 100ml solvent 4:1, the mixture of 4-dioxane and water, its volume ratio is 8: 2, heating while stirring, be warming up to 65 ℃ mixture is all dissolved, system temperature is reduced to 10 ℃, crystallization 2h under agitation condition.The crystallization of 4-nitrophthalic acid is separated out, and filters, and filter cake 45g is a 4-nitrophthalic acid crude product, and the purity of 4-nitrophthalic acid is 93.1%, and filtrate D enters vaporizer.
45g filter cake 4-nitrophthalic acid crude product is entered 4-nitrophthalic acid recrystallizer, add 1 simultaneously, 4-dioxane 50ml, heating while stirring, treat whole dissolvings, system temperature is reduced to 5 ℃, crystallization 2h under agitation condition, filter, filtration cakes torrefaction gets the 4-nitrophthalic acid product 20g of content 99.3% (wt).
In vaporizer, filtrate D is evaporated, aqueous solvent and 1, the mixture of 4-dioxane turns back in the stirring and dissolving still, and solid phase is the crude product 25g that is rich in the 3-nitrophthalic acid.
The crude product that will be rich in the 3-nitrophthalic acid again places 3-nitrophthalic acid crystallizer, add 300g water simultaneously, be warming up to dissolving fully, cool off system temperature then and reduce to 5 ℃ of post crystallizations, after the filtration, the filter cake drying gets the 3-nitrophthalic acid product 19g of purity 99.1%; Liquid phase enters in the vaporizer evaporates, and turns back to behind the water condensation in the 3-nitrophthalic acid crystallizer, and solid phase turns back to the stirring and dissolving still.
Embodiment five:
In this example, the mass ratio of 3-nitrophthalic acid and 4-nitrophthalic acid is 3: 7 in the nitro phthalandione isomer mixture.
In the stirring and dissolving still, add nitro phthalandione isomer mixture 100g and 100ml solvent 5:1, the mixture of 3-dioxolane and acetone, its volume ratio is 7: 3, heating while stirring, be warming up to 70 ℃ mixture is all dissolved, system temperature is reduced to 0 ℃, crystallization 2h under agitation condition.The crystallization of 4-nitrophthalic acid is separated out, and filters, and filter cake 45g is a 4-nitrophthalic acid crude product, and the purity of 4-nitrophthalic acid is 92.5%, and filtrate E enters vaporizer.
45g filter cake 4-nitrophthalic acid crude product is entered 4-nitrophthalic acid recrystallizer, add 1 simultaneously, 4-dioxane 50ml, heating while stirring, treat whole dissolvings, system temperature is reduced to 0 ℃, crystallization 2h under agitation condition, filter, filtration cakes torrefaction gets the 4-nitrophthalic acid product 22g of content 99.5% (wt).
In vaporizer filtrate E is evaporated, solvent 5:1, the mixture of 3-dioxolane and acetone turn back in the stirring and dissolving still, and solid phase is the crude product 22g that is rich in the 3-nitrophthalic acid.
The crude product that will be rich in the 3-nitrophthalic acid again places 3-nitrophthalic acid crystallizer, add 300g water simultaneously, be warming up to dissolving fully, cool off system temperature then and reduce to 0 ℃ of post crystallization, after the filtration, the filter cake drying gets the 3-nitrophthalic acid product 15g of purity 99.1%; Liquid phase enters in the vaporizer evaporates, and turns back to behind the water condensation in the 3-nitrophthalic acid crystallizer, and solid phase turns back to the stirring and dissolving still.
Embodiment six:
In this example, the mass ratio of 3-nitrophthalic acid and 4-nitrophthalic acid is 3: 7 in the nitro phthalandione isomer mixture.
In the stirring and dissolving still, add nitro phthalandione isomer mixture 100g and 100ml solvent 6:1,4-dioxane and alcoholic acid mixture, its volume ratio is 8: 2, heating while stirring, be warming up to 65 ℃ mixture is all dissolved, system temperature is reduced to 5 ℃, crystallization 2h under agitation condition.The crystallization of 4-nitrophthalic acid is separated out, and filters, and filter cake 53g is a 4-nitrophthalic acid crude product, and the purity of 4-nitrophthalic acid is 93.7%, and filtrate F enters vaporizer.
53g filter cake 4-nitrophthalic acid crude product is entered 4-nitrophthalic acid recrystallizer, add 1 simultaneously, 4-dioxane 50ml, heating while stirring, treat whole dissolvings, system temperature is reduced to 0 ℃, crystallization 2h under agitation condition, filter, filtration cakes torrefaction gets the 4-nitrophthalic acid product 27g of content 99.3% (wt).
In vaporizer, filtrate F is evaporated, solvent 6:1,4-dioxane and alcoholic acid mixture turn back in the stirring and dissolving still, and solid phase is the crude product 26g that is rich in the 3-nitrophthalic acid.
The crude product that will be rich in the 3-nitrophthalic acid again places 3-nitrophthalic acid crystallizer, add 300g water simultaneously, be warming up to dissolving fully, cool off system temperature then and reduce to 0 ℃ of post crystallization, after the filtration, the filter cake drying gets the 3-nitrophthalic acid product 17g of purity 99.2%; Liquid phase enters in the vaporizer evaporates, and turns back to behind the water condensation in the 3-nitrophthalic acid crystallizer, and solid phase turns back to the stirring and dissolving still.
Claims (6)
1, a kind of separation method of nitro phthalandione isomer mixture, it is characterized in that under the heating condition, with nitro phthalandione isomer mixture dissolving fully in solvent, decrease temperature crystalline is isolated crystalline 4-nitrophthalic acid crude product then; Filtrate behind the separation 4-nitrophthalic acid crude product is carried out evaporative crystallization, and solid phase is a 3-nitrophthalic acid crude product; Described solvent is 1,4-dioxane or its homologue at least any one.
2,, it is characterized in that with 4-nitrophthalic acid crude product 1, the recrystallization separation and purification obtains the 4-nitrophthalic acid in the 4-dioxane according to the separation method of the described nitro phthalandione isomer mixture of claim 1.
3,, it is characterized in that 3-nitrophthalic acid crude product is dissolved the post crystallization separation obtains the 3-nitrophthalic acid in water according to the separation method of the described nitro phthalandione isomer mixture of claim 1.
4,, it is characterized in that concrete steps are as follows according to the separation method of claim 1 or 2 or 3 described nitro phthalandione isomer mixtures:
A, in the stirring and dissolving still, add nitro phthalandione isomer mixture and solvent, be warming up to nitro phthalandione isomer mixture and dissolve fully, then decrease temperature crystalline;
B, the solidliquid mixture of a step gained is filtered, filtrate enters vaporizer, and filter cake is a 4-nitrophthalic acid crude product;
C, 4-nitrophthalic acid crude product is added 4-nitrophthalic acid recrystallizer, add solvent again, be warming up to dissolving fully, decrease temperature crystalline filters then, and the filter cake drying gets the 4-nitrophthalic acid;
D, in vaporizer the filtrate of b step is evaporated, solid phase is a 3-nitrophthalic acid crude product, and 3-nitrophthalic acid crude product is placed 3-nitrophthalic acid crystallizer;
E, in 3-nitrophthalic acid crystallizer, add entry, be warming up to fully dissolving, decrease temperature crystalline filters then, gets the crystalline filter cake, drying gets the 3-nitrophthalic acid again.
5, according to the separation method of the described nitro phthalandione isomer mixture of claim 4, it is characterized in that in vaporizer, the filtrate of e being evaporated, turn back to behind the water condensation in the 3-nitrophthalic acid crystallizer, solid phase turns back to the stirring and dissolving still.
6,, it is characterized in that service temperature in the Crystallization Separation process is that the freezing point of system is between the reflux temperature of solvent according to the separation method of the described nitro phthalandione isomer mixture of claim 1.
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