CN114853705A - Method for preparing chlorophthalic anhydride by recovering 4-chlorophthalic acid monosodium salt reaction mother liquor - Google Patents
Method for preparing chlorophthalic anhydride by recovering 4-chlorophthalic acid monosodium salt reaction mother liquor Download PDFInfo
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- CN114853705A CN114853705A CN202210432941.7A CN202210432941A CN114853705A CN 114853705 A CN114853705 A CN 114853705A CN 202210432941 A CN202210432941 A CN 202210432941A CN 114853705 A CN114853705 A CN 114853705A
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- Prior art keywords
- mother liquor
- chlorophthalic
- anhydride
- monosodium salt
- acid monosodium
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- 239000012452 mother liquor Substances 0.000 title claims abstract description 57
- UERPUZBSSSAZJE-UHFFFAOYSA-N 3-chlorophthalic anhydride Chemical compound ClC1=CC=CC2=C1C(=O)OC2=O UERPUZBSSSAZJE-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 27
- DBIOVBYLTPWVSW-UHFFFAOYSA-N 2-ethylpiperidin-4-one;hydrochloride Chemical compound Cl.CCC1CC(=O)CCN1 DBIOVBYLTPWVSW-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 230000020477 pH reduction Effects 0.000 claims abstract description 11
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 24
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 21
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 239000003208 petroleum Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229940072049 amyl acetate Drugs 0.000 claims description 3
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 3
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical class C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 abstract description 9
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 abstract description 4
- PZKLMLXRHBPLHE-UHFFFAOYSA-N 4-chlorophthalic acid;sodium Chemical compound [Na].OC(=O)C1=CC=C(Cl)C=C1C(O)=O PZKLMLXRHBPLHE-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005660 chlorination reaction Methods 0.000 abstract description 2
- 238000006298 dechlorination reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 8
- RLCCWSGPYQLVSW-UHFFFAOYSA-M sodium;3-chlorophthalate;hydron Chemical compound [Na+].OC(=O)C1=CC=CC(Cl)=C1C([O-])=O RLCCWSGPYQLVSW-UHFFFAOYSA-M 0.000 description 7
- BKFXSOCDAQACQM-UHFFFAOYSA-N 3-chlorophthalic acid Chemical class OC(=O)C1=CC=CC(Cl)=C1C(O)=O BKFXSOCDAQACQM-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- DVIPPHSQIBKWSA-UHFFFAOYSA-N 4-chlorophthalic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1C(O)=O DVIPPHSQIBKWSA-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- -1 4, 4' -biphenyl dianhydride Chemical compound 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- WRVIURJLISDSGN-UHFFFAOYSA-M sodium 2-carboxy-3,5-dichlorobenzoate Chemical compound [Na+].OC(=O)c1c(Cl)cc(Cl)cc1C([O-])=O WRVIURJLISDSGN-UHFFFAOYSA-M 0.000 description 1
- QYJGVABVTPTRNZ-UHFFFAOYSA-M sodium 2-carboxy-3,6-dichlorobenzoate Chemical compound [Na+].OC(=O)c1c(Cl)ccc(Cl)c1C([O-])=O QYJGVABVTPTRNZ-UHFFFAOYSA-M 0.000 description 1
- HPLDORJJVPSYGH-UHFFFAOYSA-M sodium;2-carboxy-3,4-dichlorobenzoate Chemical compound [Na+].OC(=O)C1=C(Cl)C(Cl)=CC=C1C([O-])=O HPLDORJJVPSYGH-UHFFFAOYSA-M 0.000 description 1
- DSGYKFHTOCXJAB-UHFFFAOYSA-M sodium;2-carboxy-4,5-dichlorobenzoate Chemical compound [Na+].OC(=O)C1=CC(Cl)=C(Cl)C=C1C([O-])=O DSGYKFHTOCXJAB-UHFFFAOYSA-M 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a method for recovering and preparing chlorophthalic anhydride from 4-chlorophthalic acid monosodium salt reaction mother liquor, belonging to the field of organic synthesis. The invention provides a method for preparing chlorophthalic anhydride by recovering 4-chlorophthalic acid monosodium salt reaction mother liquor, which comprises the following steps: mixing the 4-chlorophthalic acid monosodium salt reaction mother liquor with inorganic acid for acidification to obtain acidified mother liquor; extracting the acidified mother liquor by using an extracting agent to obtain an oil layer; and concentrating the oil layer to obtain the chlorophthalic anhydride. The method recycles the chlorinated organic matters in the 4-chlorophthalic acid monosodium mother liquor and prepares the chlorinated phthalic anhydride, the ring-closing rate of the chlorinated organic matters reaches over 99.5 percent, the chlorinated organic matters have utilizable value, and the chlorinated organic matters can be used for dechlorination to prepare phthalic anhydride or chlorination to prepare perchlorophthalic anhydride.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for preparing chlorophthalic anhydride by recovering 4-chlorophthalic acid monosodium salt reaction mother liquor.
Background
The 4-chlorophthalic acid monosodium salt is one of the main raw materials for preparing 3,3 ', 4, 4' -diphenyl ether dianhydride.
3,3 ', 4, 4' -biphenyl dianhydride is an important monomer for synthesizing polyimide, the polyimide is an excellent high-temperature resistant material, has good mechanical property, dielectric property, radiation resistance, solvent resistance and the like, has wide application in the electronic industry, and the demand of polyimide electronic materials is increased year by year along with the development of 5G technology and flexible screen display.
The preparation method of the chlorophthalic acid monosodium salt mainly comprises a chlorine introducing method of phthalic anhydride and a sodium hypochlorite dripping method of phthalic anhydride, for example, Chinese patent CN1824638A discloses a chlorine introducing method, and CN110563678A discloses a sodium hypochlorite dripping method. Both the chlorine introduction method and the sodium hypochlorite dropping method can generate a large amount of reaction mother liquor, and the mother liquor contains a large amount of chlorophthalic acid monosodium salt and inorganic salt, so that the treatment cost of the mother liquor as wastewater is high, and the loss of organic matters is caused.
Disclosure of Invention
In view of the above, the invention aims to provide a method for recovering and preparing chlorophthalic anhydride from 4-chlorophthalic acid monosodium salt reaction mother liquor. The invention recovers the chlorinated organic matters in the 4-chlorophthalic acid monosodium mother liquor and prepares the chlorinated phthalic anhydride, the ring-closing rate of the chlorinated phthalic anhydride reaches more than 99.5 percent, and the chlorinated phthalic anhydride has utilizable value.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for preparing chlorophthalic anhydride by recovering 4-chlorophthalic acid monosodium salt reaction mother liquor, which comprises the following steps:
mixing the 4-chlorophthalic acid monosodium salt reaction mother liquor with inorganic acid for acidification to obtain acidified mother liquor;
extracting the acidified mother liquor by using an extracting agent to obtain an oil layer;
and concentrating the oil layer to obtain the chlorophthalic anhydride.
Preferably, the inorganic acid is hydrochloric acid or sulfuric acid.
Preferably, the pH value of the acidification end point is 0.01-1.0, and the acidification mother liquor is in a clear solution state.
Preferably, the extractant includes petroleum ether and acetate type extractants.
Preferably, the acetate extractant includes one or more of butyl acetate and isomers thereof, amyl acetate and isomers thereof, and hexyl acetate and isomers thereof.
Preferably, the mass ratio of the petroleum ether to the acetate extractant in the extractant is 1: 5-10.
Preferably, the dosage of the extracting agent is 0.2-2 times of the mass of the 4-chlorophthalic acid monosodium salt reaction mother liquor.
Preferably, the temperature of the extraction is 10-50 ℃.
Preferably, the concentration comprises sequentially recovering the extractant and dehydrating.
Preferably, the vacuum degree of the recovered extractant is 30-70 KPa, and the temperature is 60-150 ℃; the vacuum degree of dehydration is 0-500 Pa, and the temperature is 150-240 ℃.
The invention provides a method for preparing chlorophthalic anhydride by recovering 4-chlorophthalic acid monosodium salt reaction mother liquor, which comprises the following steps: mixing the 4-chlorophthalic acid monosodium salt reaction mother liquor with inorganic acid for acidification to obtain acidified mother liquor; extracting the acidified mother liquor by using an extracting agent to obtain an oil layer; and concentrating the oil layer to obtain the chlorophthalic anhydride.
The method recycles the chlorinated organic matters in the 4-chlorophthalic acid monosodium mother liquor and prepares the chlorinated phthalic anhydride, the ring-closing rate of the chlorinated organic matters reaches over 99.5 percent, the chlorinated organic matters have utilizable value, and the chlorinated organic matters can be used for dechlorination to prepare phthalic anhydride or chlorination to prepare perchlorophthalic anhydride.
Furthermore, the mother liquor after back extraction only contains inorganic salt, thereby greatly reducing the cost of environmental protection treatment.
The preparation method provided by the invention is simple to operate, low in cost and suitable for industrial production.
Detailed Description
The invention provides a method for preparing chlorophthalic anhydride by recovering 4-chlorophthalic acid monosodium salt reaction mother liquor, which comprises the following steps:
mixing the 4-chlorophthalic acid monosodium salt reaction mother liquor with inorganic acid for acidification to obtain acidified mother liquor;
extracting the acidified mother liquor by using an extracting agent to obtain an oil layer;
and concentrating the oil layer to obtain the chlorophthalic anhydride.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The method mixes the 4-chlorophthalic acid monosodium salt reaction mother liquor with inorganic acid for acidification to obtain the acidified mother liquor.
In the invention, the structural formula of the monosodium salt of 4-chlorophthalic acid in the monosodium salt reaction mother liquor of 4-chlorophthalic acid is shown as formula 1, and the structural formulas of other main monosodium salts of chlorophthalic acid are shown as formulas 2-6:
In the present invention, the inorganic acid is preferably hydrochloric acid or sulfuric acid. The concentration of the inorganic acid in the present invention is not particularly limited, and may be a concentration known to those skilled in the art.
In the invention, the pH value of the acidification end point is preferably 0.01-1.0, and the acidification mother liquor is preferably in a clear solution state.
After obtaining the acidified mother liquor, the invention extracts the acidified mother liquor by using an extractant to obtain an oil layer.
In the present invention, the extractant preferably comprises petroleum ether and acetate type extractants.
In the present invention, the acetate-based extractant preferably includes one or more of butyl acetate and isomers thereof, amyl acetate and isomers thereof, and hexyl acetate and isomers thereof, and more preferably butyl acetate.
In the invention, the mass ratio of the petroleum ether to the acetate extractant in the extractant is preferably 1: 5-10, more preferably 1: 6-8, and even more preferably 1: 7.
In the invention, the dosage of the extracting agent is preferably 0.2-2 times, more preferably 0.5-1.5 times, and even more preferably 1.0 time of the mass of the 4-chlorophthalic acid monosodium salt reaction mother liquor.
In the invention, the extraction temperature is preferably 10-50 ℃, more preferably 20-40 ℃, and further preferably 30 ℃.
In the invention, in the extraction process, organic matters enter the oil layer, inorganic salt enters the water layer, and the recovered mother liquor only contains inorganic salt, so that the environmental protection treatment cost is greatly reduced.
In the invention, the water layer preferably enters an MVR salt evaporation system to produce salt, the salt is sold as byproduct salt, and the evaporated water can be recycled to production as primary water.
In the present invention, the concentration preferably includes recovering the extractant and dehydrating in this order.
In the invention, the vacuum degree of the recovered extractant is preferably 30-70 KPa, more preferably 40-60 KPa, the temperature is preferably 60-150 ℃, more preferably 80-130 ℃, and the recovered extractant is preferably vacuum distillation; the vacuum degree of the dehydration is preferably 0-500 Pa, more preferably 0-200 Pa, the temperature is preferably 150-240 ℃, more preferably 180-220 ℃, and the dehydration is preferably vacuum distillation.
In the invention, the chlorophthalic acid is dehydrated at high temperature in the dehydration process to generate chlorophthalic anhydride, and then the chlorophthalic anhydride is distilled at high temperature to form fraction which is evaporated and condensed to form a finished chlorophthalic anhydride product.
In the invention, the solvent obtained by recovering the extracting agent is recycled for extraction.
In order to further illustrate the present invention, the method for recovering and preparing chlorophthalic anhydride from the reaction mother liquor of 4-chlorophthalic acid monosodium salt provided by the present invention is described in detail below with reference to examples, which should not be construed as limiting the scope of the present invention.
Example 1
Putting 1000g of 4-chlorophthalic acid monosodium salt reaction mother liquor (containing 7 wt% of chlorophthalic acid monosodium salt) into a 2000L reaction bottle, stirring at normal temperature, dropwise adding hydrochloric acid into the mother liquor until the materials in the mother liquor are completely dissolved and clarified, detecting the pH value to be 0.48, adding 1000g of mixed extracting agent of petroleum ether and butyl acetate, wherein the weight of the petroleum ether is 125g and the weight of the butyl acetate is 875g, heating to 30 ℃, stirring and extracting for 1h, standing for 0.5h, separating, distilling under reduced pressure of an oil layer, controlling the vacuum degree to be 50MKa, distilling butyl acetate to recover, continuously distilling under reduced pressure of a concentrated oil layer, controlling the vacuum degree to be 100-200 Pa, after distilling a small amount of butyl acetate in the concentrated solution, switching fractions to evaporate organic materials, dehydrating chlorophthalic acid to generate chlorophthalic anhydride in the distillation process, collecting organic fractions to obtain the chlorophthalic anhydride, and the closed loop rate is detected to be 99.65%. 965g of recovered extractant and 65g of discharged chlorophthalic anhydride.
Example 2
Putting 1000g of 4-chlorophthalic acid monosodium salt reaction mother liquor (containing 7 wt% of chlorophthalic acid monosodium salt) into a 2000L reaction bottle, stirring at normal temperature, dropwise adding hydrochloric acid into the mother liquor until the materials in the mother liquor are completely dissolved and clarified, detecting the pH value of 0.35, adding 500g of mixed extracting agent of petroleum ether and butyl acetate, wherein the weight of the petroleum ether is 63g and the weight of the butyl acetate is 437g, heating to 30 ℃, stirring and extracting for 1h, standing for 0.5h, separating, distilling under reduced pressure, controlling the vacuum degree to be 50MKa, distilling butyl acetate out for recycling, continuously distilling under reduced pressure for a concentrated oil layer, controlling the vacuum degree to be 100-200 Pa, after a small amount of butyl acetate in the concentrated solution is distilled out, switching fractions to evaporate organic materials, dehydrating chlorophthalic acid in the distillation process to generate chlorophthalic anhydride, collecting organic fractions to obtain the chlorophthalic anhydride, the closed loop rate is detected to be 99.56%. The recovery amount of the extracting agent is 470g, and the discharge amount of the chlorophthalic anhydride is 60 g.
Example 3
Putting 1000g of 4-chlorophthalic acid monosodium salt reaction mother liquor (containing 7 wt% of chlorophthalic acid monosodium salt) into a 2000L reaction bottle, stirring at normal temperature, dropwise adding hydrochloric acid into the mother liquor until the materials in the mother liquor are completely dissolved and clarified, detecting the pH value to be 0.28, adding 1000g of mixed extracting agent of petroleum ether and butyl acetate, wherein the weight of the petroleum ether is 125g and the weight of the butyl acetate is 875g, heating to 50 ℃, stirring and extracting for 1h, standing for 0.5h, separating, distilling under reduced pressure of an oil layer, controlling the vacuum degree to be 50MKa, distilling butyl acetate to recover, continuously distilling under reduced pressure of a concentrated oil layer, controlling the vacuum degree to be 100-200 Pa, after distilling a small amount of butyl acetate in the concentrated solution, switching fractions to evaporate organic materials, dehydrating chlorophthalic acid in the distillation process to generate chlorophthalic anhydride, collecting organic fractions to obtain the chlorophthalic anhydride, and the closed loop rate is detected to be 99.63%. The yield of butyl acetate was 955g, and the yield of chlorophthalic anhydride was 62 g.
Comparative example 1 (Single extractant butyl acetate)
Putting 1000g of 4-chlorophthalic acid monosodium salt reaction mother liquor (containing 7 wt% of chlorophthalic acid monosodium salt) into a 2000L reaction bottle, stirring at normal temperature, dropwise adding hydrochloric acid into the mother liquor until the materials in the mother liquor are completely dissolved and clarified, detecting the pH value of 0.48, adding 1000g of butyl acetate extractant, heating to 30 ℃, stirring and extracting for 1h, standing for 0.5h, separating, distilling an oil layer under reduced pressure, controlling the vacuum degree to be 50MKa, distilling butyl acetate out for recycling, continuously distilling the concentrated oil layer under reduced pressure, controlling the vacuum degree to be 100-200 Pa, distilling a small amount of butyl acetate out of a concentrated solution, switching fractions to evaporate organic materials, dehydrating chlorophthalic acid in the distillation process to generate chlorophthalic anhydride, collecting the organic fractions to be chlorophthalic anhydride, and detecting the ring-closing rate to be 99.55%. The recovery amount of the extracting agent is 960g, and the discharge amount of the chlorophthalic anhydride is 55 g. The material yield of the final product is low and the extraction effect is poor.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (10)
1. A method for recovering and preparing chlorophthalic anhydride from 4-chlorophthalic acid monosodium salt reaction mother liquor is characterized by comprising the following steps:
mixing the 4-chlorophthalic acid monosodium salt reaction mother liquor with inorganic acid for acidification to obtain acidified mother liquor;
extracting the acidified mother liquor by using an extracting agent to obtain an oil layer;
and concentrating the oil layer to obtain the chlorophthalic anhydride.
2. The method according to claim 1, wherein the inorganic acid is hydrochloric acid or sulfuric acid.
3. The method according to claim 1 or 2, wherein the pH at the end of the acidification is 0.01 to 1.0, and the acidified mother liquor is in a clear solution state.
4. The method of claim 1, wherein the extractant comprises petroleum ether and acetate extractants.
5. The method of claim 4, wherein the acetate extractant comprises one or more of butyl acetate and its isomers, amyl acetate and its isomers, and hexyl acetate and its isomers.
6. The preparation method according to claim 4 or 5, wherein the mass ratio of the petroleum ether to the acetate extractant in the extractant is 1: 5-10.
7. The preparation method according to claim 1, 4 or 5, wherein the amount of the extractant is 0.2-2 times of the mass of the 4-chlorophthalic acid monosodium salt reaction mother liquor.
8. The method according to claim 1, wherein the temperature of the extraction is 10 to 50 ℃.
9. The method of claim 1, wherein the concentrating comprises sequentially recovering the extractant and dehydrating.
10. The preparation method of claim 9, wherein the vacuum degree of the recovered extractant is 30 to 70KPa, and the temperature is 60 to 150 ℃; the vacuum degree of dehydration is 0-500 Pa, and the temperature is 150-240 ℃.
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|---|---|---|---|---|
| GB347666A (en) * | 1929-12-24 | 1931-04-24 | Philip Fletcher Bangham | Improvements in and relating to the production of halogen phthalic anhydrides |
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| DE2814947A1 (en) * | 1977-04-06 | 1978-10-12 | Mitsui Toatsu Chemicals | CHLORINATED 4-METHYLPHTHALIC ACIDS AND THEIR ANHYDRIDES AND THE METHOD FOR THEIR PRODUCTION |
| CN1526710A (en) * | 2003-09-25 | 2004-09-08 | 华东师范大学 | Prepn of 4-chlorophthalic anhydride |
| JP2006213646A (en) * | 2005-02-03 | 2006-08-17 | Mitsubishi Chemicals Corp | Method for producing oxydiphthalic anhydride |
| CN104496951A (en) * | 2015-01-11 | 2015-04-08 | 景炜杰 | Preparation method of chlorophthalic anhydride |
| CN110563678A (en) * | 2019-10-15 | 2019-12-13 | 上海固创化工新材料有限公司 | Preparation method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride |
| CN111620769A (en) * | 2020-06-04 | 2020-09-04 | 南通汇顺化工有限公司 | Method for preparing 3,3 ', 4, 4' -biphenyl tetracarboxylic dianhydride |
-
2022
- 2022-04-24 CN CN202210432941.7A patent/CN114853705A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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