CN114014750B - Method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor - Google Patents
Method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor Download PDFInfo
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- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 31
- 239000012452 mother liquor Substances 0.000 title claims abstract description 30
- 238000004821 distillation Methods 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 23
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 19
- 239000002910 solid waste Substances 0.000 claims abstract description 11
- -1 decolorizing Substances 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 3
- 238000000643 oven drying Methods 0.000 claims abstract description 3
- 239000010413 mother solution Substances 0.000 claims abstract 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 13
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 229920002472 Starch Polymers 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 6
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 6
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 238000003916 acid precipitation Methods 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 19
- 239000007788 liquid Substances 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- SIVYRLBDAPKADZ-UHFFFAOYSA-N 4-methylnaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C)=CC=C(C(O)=O)C2=C1 SIVYRLBDAPKADZ-UHFFFAOYSA-N 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000008247 solid mixture Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- KTPCEPWBURBLPQ-UHFFFAOYSA-N 4-(hydroxymethyl)naphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(CO)=CC=C(C(O)=O)C2=C1 KTPCEPWBURBLPQ-UHFFFAOYSA-N 0.000 description 1
- INKOQGZWHUTYIW-UHFFFAOYSA-N 4-formylnaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C=O)C2=C1 INKOQGZWHUTYIW-UHFFFAOYSA-N 0.000 description 1
- PSAGPCOTGOTBQB-UHFFFAOYSA-N 4-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(O)C2=C1 PSAGPCOTGOTBQB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229940094035 potassium bromide Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/295—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with inorganic bases, e.g. by alkali fusion
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of a 1, 4-naphthalene dicarboxylic acid reaction mother solution, which comprises the following steps: firstly adding water into distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor, then adding alkali liquor to adjust the pH to 12-14, heating to 45-55 ℃ to enable the mixture to be completely dissolved, then adjusting the pH of the solution to 3, centrifuging to obtain solid waste, extracting the centrifuged solution with an organic solvent to obtain tar, adding alkali liquor into an extracted water layer to adjust the pH to 10-12, heating to 60-70 ℃ and adding sodium hypochlorite solution, and carrying out heat preservation treatment after the addition is finished; removing excessive sodium hypochlorite, decolorizing, acid separating, spin-drying and oven-drying to obtain 1, 4-naphthalene dicarboxylic acid. The recovery method disclosed by the invention is simple in procedure and easy to operate, and accords with the concept of green and environment-friendly. The content of the recovered product is up to 99.3% by using the method of the invention.
Description
Technical Field
The invention belongs to the field of recovery of 1, 4-naphthalene dicarboxylic acid, and particularly relates to a method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of reaction mother liquor of 1, 4-naphthalene dicarboxylic acid.
Background
In the patent CN103739484A, 1-methyl-4-naphthoic acid is taken as a starting material, glacial acetic acid is taken as a solvent, cobalt acetate, manganese acetate and potassium bromide are taken as catalysts, in the preparation of 1, 4-naphthalene dicarboxylic acid by catalytic oxygen oxidation reaction, after a plurality of times of application of glacial acetic acid mother liquor, decarboxylates, ring-breaking substances and generated tar are accumulated more and more in oxygen oxidation, 1-methyl-4-naphthoic acid cannot be continuously added even if activated carbon is adsorbed, a main raw material 1-methyl-4-naphthoic acid is added in the normal reaction, the catalyst and acetic anhydride are required to be added to convert moisture in the mother liquor into glacial acetic acid to enable the chemical reaction to be carried out in the positive reaction direction, and then oxygen is introduced to carry out oxidation reaction, so that if a plurality of batches of tar react are accumulated more, the catalyst is poisoned and only distilled treatment is carried out; the solid mixture obtained by distillation contains decarboxylates, ring-broken substances, a small amount of raw material 1-methyl-4-naphthoic acid, intermediate 1-carboxyl-4-naphthaldehyde, intermediate 1-carboxyl-4-naphthalenyl methanol, product 1, 4-naphthalene dicarboxylic acid and tar generated in oxygen oxidation, and the current general treatment is to sell the solid mixture as solid waste to solid waste treatment units with treatment qualification, and 4800 yuan per ton of payment. How to remove decarboxylate, ring-broken matter and tar in solid waste, remove a small amount of unreacted raw materials, change the intermediate product 1-carboxyl-4-naphthaline methanol into 1, 4-naphthalene dicarboxylic acid, change the intermediate product 1-carboxyl-4-naphthaline formaldehyde into 1, 4-naphthalene dicarboxylic acid, simultaneously take out the 1, 4-naphthalene dicarboxylic acid in solid mixture, separate and purify the 1, 4-naphthalene dicarboxylic acid consistent with the product in the prior batch from the solid mixture, and become the problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor, which fully utilizes the mother liquor for preparing 1, 4-naphthalene dicarboxylic acid in the prior art, recovers the 1, 4-naphthalene dicarboxylic acid and reduces solid waste.
The aim of the invention is achieved by the following technical scheme:
a method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor comprises the following steps:
firstly, adding water into distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor, then adding alkali liquor to adjust the pH to 12-14, heating to 45-55 ℃ to enable the mixture to be completely dissolved, then adjusting the pH of the solution to 3, centrifuging to obtain solid waste, extracting the centrifuged solution with an organic solvent to obtain tar, adding alkali liquor into an extracted water layer to adjust the pH to 10-12, heating to 60-70 ℃ and adding sodium hypochlorite solution, and carrying out heat preservation treatment after the addition is finished; removing excessive sodium hypochlorite, decolorizing, acid separating, spin-drying and oven-drying to obtain 1, 4-naphthalene dicarboxylic acid.
Preferably, the alkali liquor is 30-32 wt% sodium hydroxide solution.
Preferably, the organic solvent is at least one of chloroform, toluene and 1, 2-dichloroethane.
Preferably, the concentration of the sodium hypochlorite solution is 8 to 12wt%, more preferably 10wt%.
Preferably, the volume mass ratio of the adding amount of the sodium hypochlorite solution to the distillation residues of the 1, 4-naphthalene dicarboxylic acid reaction mother liquor is 2.5-2.7L/kg.
Preferably, the time of the heat preservation treatment is 1 to 1.5 hours.
Preferably, the mode of removing the redundant sodium hypochlorite is as follows: excess sodium hypochlorite was removed using a 10wt% aqueous sodium metabisulfite solution, and the test starch potassium iodide paper was kept from turning blue.
Preferably, the decoloring mode is as follows: 10wt% dilute sulfuric acid is used to adjust the PH=6.5, active carbon is added, and the mixture is stirred and decolorized for 40 minutes at 75-85 ℃ and filtered to obtain a solution.
Preferably, the acid precipitation mode is as follows: the decolorized solution is heated to 95-98 ℃, and 10wt% of dilute sulfuric acid is added to adjust the PH=1.
Preferably, the spin-drying and drying modes are as follows: cooling the solution after acid precipitation to 60 ℃ and spin-drying, then rinsing with water until the PH of the washing water is=5, and finally spin-drying again and then drying.
The mechanism involved in the invention is as follows:
adding water into the distillation residues of the 1, 4-naphthalene dicarboxylic acid reaction mother liquor, adding alkali liquor, heating to dissolve the residues, and adjusting the pH to 3, wherein the pH is 3, so that impurities cannot be removed too high, and products can be separated out too low; at the pH value, decarboxylate and ring-breaking compound are removed, a small amount of unreacted raw material 1-methyl-4-naphthoic acid can be separated out as solid, and two intermediate products 1-carboxyl-4-naphthol alcohol, 1-carboxyl-4-naphthol aldehyde and 1, 4-naphthalene dicarboxylic acid are all in the form of sodium salt in aqueous solution, centrifugal drying is carried out to obtain solid waste, the aqueous solution is used for extracting light tar (some oily substances), alkali liquor is added into the aqueous layer to adjust the alkali liquor to be alkaline, sodium hypochlorite is added into the aqueous layer to react alcoholic hydroxyl groups and aldehyde groups of the two intermediate products into sodium carboxylate, and then decoloration, acid precipitation, drying and drying are carried out to obtain qualified finished product 1, 4-naphthalene dicarboxylic acid.
Compared with the prior art, the invention has the beneficial effects that:
the invention designs a set of method for recovering 1, 4-naphthalene dicarboxylic acid from residues aiming at distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor, and the recovery method has simple procedures and easy operation and accords with the concept of environmental protection in the current stage. The content of the recovered product is up to 99.3% by using the method of the invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The liquid base described in the examples is a sodium hydroxide solution having a concentration of 30% by weight.
Example 1
A method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor comprises the following steps:
adding 150kg of wet 1, 4-naphthalene dicarboxylic acid reaction mother liquor distillation residues, 1200kg of water and 180L of liquid alkali into a 2000L kettle, heating to 45 ℃ to dissolve materials, retesting PH=14, regulating PH=3 with 10wt% of dilute sulfuric acid, putting into a centrifuge to spin dry to obtain solid, 50kg of solid is solid waste, adding the mother liquor into the 3000L kettle, adding 600L of chloroform, stirring for 30 minutes, standing for 30 minutes, separating a lower chloroform layer to recycle a chloroform sleeve for next batch, adding 150L of liquid alkali into the water layer to regulate PH=10, heating to 60 ℃, dropwise adding 400L of 10wt% sodium hypochlorite at 60 ℃, keeping the temperature for 1 hour after the dropwise, removing excessive sodium hypochlorite with 10wt% of sodium metabisulfite aqueous solution (the starch iodide for testing is not changed into blue, regulating PH=6.5 with 10wt% of dilute sulfuric acid), adding 3kg of active carbon, stirring at 75 ℃ for 40 minutes, stirring, heating to 95 ℃, dropwise adding 10% of dilute sulfuric acid at 95 ℃, regulating PH=1, cooling to 60 ℃, eluting to the temperature, and cooling to the temperature until the pH=5 is consistent with that of the water content of the water is equal to that of the water content of the water in the 3000L kettle (the water is equal to that of the white product is not changed to 3kg of the water, and the white product is obtained after the white product is washed by the water, and the white product is washed by the water is washed (the water is 3, and the white product is 3) and the white water is washed and the white product is 3) and the quality is washed by the quality 3).
Example 2
A method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor comprises the following steps:
adding 155kg of wet 1, 4-naphthalene dicarboxylic acid reaction mother liquor distillation residues, 1210kg of water and 180L of liquid alkali into a 2000L kettle, heating to 55 ℃ to dissolve materials, retesting PH=14, regulating PH=3 with 10wt% of dilute sulfuric acid, putting into a centrifuge to spin dry to obtain solid, 52kg of solid waste, adding 600L of toluene into the 3000L kettle, stirring for 30 minutes, standing for 30 minutes, separating a lower toluene layer to recycle toluene jacket for next batch, adding 150L of liquid alkali into the water layer to regulate PH=11, heating to 70 ℃, dropwise adding 402L of 10wt% of sodium hypochlorite at 70 ℃, keeping the temperature for 1 hour after the dropwise adding, removing excessive sodium hypochlorite with 10wt% of sodium metabisulfite aqueous solution (the starch iodide for testing is not changed into blue, standard), regulating PH=6.5 with 10wt% of dilute sulfuric acid, adding 3kg of active carbon, stirring at 85 ℃ for 40 minutes, stirring, heating to 98 ℃, dropwise adding 10% of dilute sulfuric acid at 98 ℃ to regulate PH=1, cooling to 60 ℃, eluting to obtain a white product with the same appearance as that of water content as that of the water for the next batch (the water content is equal to 99.0 kg of the white product is obtained after the water is washed by the water and the water is equal to 1 kg of the water for the product is washed by the normal drying).
Examples 3
A method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor comprises the following steps:
adding 148kg of wet 1, 4-naphthalene dicarboxylic acid reaction mother liquor distillation residues, 1200kg of water and 180L of liquid alkali into a 2000L kettle, heating to 50 ℃ to dissolve materials, retesting PH=14, adjusting PH=3 with 10wt% of dilute sulfuric acid, putting into a centrifuge for spin-drying to obtain solid, adding 49kg of solid into a 3000L kettle as solid waste, adding 580L1,2-dichloroethane, stirring for 30 minutes, standing for 30 minutes, separating a lower layer of 1, 2-dichloroethane layer, recovering 1, 2-dichloroethane for next batch, adding 150L of liquid alkali into a water layer to adjust PH=11, heating to 68 ℃, dripping 400L of 10wt% sodium hypochlorite at 68 ℃, after the dripping, keeping the temperature for 1.5 hours, removing excessive sodium hypochlorite by using 10wt% of sodium metabisulfite aqueous solution (the test starch potassium iodide test paper does not change into blue), regulating the PH=6.5 by using 10wt% of dilute sulfuric acid, adding 2.8kg of active carbon, stirring, decoloring at 80 ℃ for 40 minutes, filtering into another 3000L kettle, stirring, heating to 98 ℃, dripping 10% of dilute sulfuric acid at 98 ℃ to regulate the PH=1, cooling to 60 ℃, spin-drying, rinsing with water until the washing water PH=5 on a centrifuge, spin-drying and drying to obtain 57.3kg of 1, 4-naphthalene dicarboxylic acid (which is consistent with the product in the prior batch), and obtaining the product which is white in appearance and has 99.2 percent of content and is consistent with the product in the prior batch.
Example 4
A method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor comprises the following steps:
adding 152kg of wet 1, 4-naphthalene dicarboxylic acid reaction mother liquor distillation residues, 1200kg of water and 183L of liquid alkali into a 2000L kettle, heating to 48 ℃ to dissolve materials, retesting PH=14, regulating PH=3 by using 10wt% dilute sulfuric acid, putting into a centrifuge for spin-drying to obtain solid, 51.5kg of solid is solid waste, adding 600L of toluene into the 3000L kettle, stirring for 30 minutes, standing for 30 minutes, separating a lower toluene layer to recycle toluene for next batch, adding 150L of liquid alkali into a water layer to regulate PH=11, heating to 68 ℃, dropwise adding 402L of 10wt% sodium hypochlorite at 68 ℃, keeping the temperature for 1 hour after the dropwise adding, heating to 10wt% sodium metabisulfite aqueous solution to remove excessive sodium hypochlorite (the test starch potassium iodide test paper does not become blue), regulating PH=6.5 by using 10wt% dilute sulfuric acid, adding 3.5kg of active carbon, stirring at 85 ℃ for decolorizing 40 minutes, filtering into another 3000L kettle, stirring to 95 ℃, dropwise adding 10% dilute sulfuric acid at 95 ℃ to regulate PH=1, cooling to 60 ℃, and cooling to 60 ℃ until the PH=5, and the water content is consistent with that of the water content of the water is equal to that of the water content of the naphthalene dicarboxylic acid in the water in the kettle (the water is equal to that of the water content of the water of 1.8 kg and the water is equal to the 8.0 kg) in the white product, and the white product is obtained after the drying.
The above-described embodiments of the present invention do not limit the scope of the present invention. Any other corresponding changes and modifications made in accordance with the technical idea of the present invention shall be included in the scope of the claims of the present invention.
Claims (7)
1. A method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of reaction mother liquor of 1, 4-naphthalene dicarboxylic acid, which is characterized by comprising the following steps:
firstly, adding water into distillation residues of a 1, 4-naphthalene dicarboxylic acid reaction mother solution, then adding alkali liquor to adjust the pH to 12-14, heating to 45-55 ℃ to enable the mixture to be completely dissolved, then adjusting the pH of the solution to 3, centrifuging, obtaining solid after centrifuging to be solid waste, extracting the centrifuged solution with an organic solvent to obtain tar, adding alkali liquor into an extracted water layer to adjust the pH to 10-12, heating to 60-70 ℃ and adding sodium hypochlorite solution, and carrying out heat preservation treatment after the addition is finished; removing excessive sodium hypochlorite, decolorizing, acid separating, spin-drying and oven-drying to obtain 1, 4-naphthalene dicarboxylic acid;
the volume-mass ratio of the addition amount of the sodium hypochlorite solution to the distillation residues of the 1, 4-naphthalene dicarboxylic acid reaction mother liquor is 2.5-2.7L/kg;
the concentration of the sodium hypochlorite solution is 8-12wt%;
the organic solvent is at least one of chloroform, toluene and 1, 2-dichloroethane.
2. The method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor according to claim 1, wherein the alkali liquor is 30-32wt% sodium hydroxide solution.
3. The method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of 1, 4-naphthalene dicarboxylic acid reaction mother liquor according to claim 1, wherein the heat preservation treatment time is 1-1.5 h.
4. The method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of a reaction mother liquor of 1, 4-naphthalene dicarboxylic acid according to claim 1, wherein the method for removing excess sodium hypochlorite comprises the following steps: excess sodium hypochlorite was removed using a 10wt% aqueous sodium metabisulfite solution, and the test starch potassium iodide paper was kept from turning blue.
5. The method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of reaction mother liquor of 1, 4-naphthalene dicarboxylic acid according to claim 1, wherein the decoloring mode is as follows: and adjusting the PH=6.5 by adopting 10wt% of dilute sulfuric acid, adding active carbon, stirring at 75-85 ℃ for decoloration for 40 minutes, and filtering to obtain a solution.
6. The method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of reaction mother liquor of 1, 4-naphthalene dicarboxylic acid according to claim 1, wherein the acid precipitation mode is as follows: and heating the decolorized solution to 95-98 ℃, and adding 10wt% of dilute sulfuric acid to adjust the PH=1.
7. The method for separating and purifying 1, 4-naphthalene dicarboxylic acid from distillation residues of reaction mother liquor of 1, 4-naphthalene dicarboxylic acid according to claim 1, wherein the spin-drying and drying modes are as follows: cooling the solution after acid precipitation to 60 ℃ and spin-drying, then rinsing with water until the PH of the washing water is=5, and finally spin-drying again and then drying.
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