CN114014750A - Method for separating and purifying 1, 4-naphthalenedicarboxylic acid from distillation residue of 1, 4-naphthalenedicarboxylic acid reaction mother liquor - Google Patents
Method for separating and purifying 1, 4-naphthalenedicarboxylic acid from distillation residue of 1, 4-naphthalenedicarboxylic acid reaction mother liquor Download PDFInfo
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- CN114014750A CN114014750A CN202111435360.0A CN202111435360A CN114014750A CN 114014750 A CN114014750 A CN 114014750A CN 202111435360 A CN202111435360 A CN 202111435360A CN 114014750 A CN114014750 A CN 114014750A
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- naphthalenedicarboxylic acid
- mother liquor
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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 70
- 239000012452 mother liquor Substances 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 34
- 238000004821 distillation Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005708 Sodium hypochlorite Substances 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 19
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 239000002910 solid waste Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- -1 decoloring Substances 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims abstract description 3
- 230000001376 precipitating effect Effects 0.000 claims abstract description 3
- 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
- 239000000243 solution Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 12
- 238000012360 testing method Methods 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
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000001816 cooling Methods 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
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 238000003916 acid precipitation Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 15
- 239000007788 liquid Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000013067 intermediate product 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
- 230000008859 change Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture 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
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006114 decarboxylation reaction Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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
- 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
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- 230000007547 defect 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
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940094035 potassium bromide Drugs 0.000 description 1
- 239000008237 rinsing water Substances 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
Landscapes
- 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-naphthalenedicarboxylic acid from distillation residues of 1, 4-naphthalenedicarboxylic acid reaction mother liquor, which comprises the following steps: firstly, adding water into 1, 4-naphthalenedicarboxylic acid reaction mother liquor distillation residues, then adding alkali liquor to adjust the pH value to 12-14, heating to 45-55 ℃ to completely dissolve the residues, then adjusting the pH value of the solution to 3, obtaining solid waste after centrifugation, extracting the centrifuged solution with an organic solvent to obtain tar, adding alkali liquor into an extracted water layer to adjust the pH value to 10-12, heating to 60-70 ℃, adding a sodium hypochlorite solution, and carrying out heat preservation treatment after the addition is finished; removing redundant sodium hypochlorite, decoloring, acid precipitating, spin-drying and drying to obtain the 1, 4-naphthalenedicarboxylic acid. The recovery method disclosed by the invention is simple in process and easy to operate, and accords with the concept of environmental protection. By using the method of the invention, the content of the recovered product reaches up to 99.3 percent.
Description
Technical Field
The invention belongs to the field of 1, 4-naphthalenedicarboxylic acid recovery, and particularly relates to a method for separating and purifying 1, 4-naphthalenedicarboxylic acid from distillation residues of 1, 4-naphthalenedicarboxylic acid reaction mother liquor.
Background
Patent CN103739484A uses 1-methyl-4-naphthoic acid as a starting material, glacial acetic acid as a solvent, cobalt acetate, manganese acetate and potassium bromide as a catalyst, when 1, 4-naphthalenedicarboxylic acid is prepared by catalyzing oxygen oxidation reaction, after glacial acetic acid mother liquor is used repeatedly, decarboxylates, ring-broken products and generated tar are accumulated more in the oxygen oxidation, 1-methyl-4-naphthoic acid cannot be continuously added even if activated carbon is adsorbed, 1-methyl-4-naphthoic acid as a main raw material is added in normal reaction, a catalyst and acetic anhydride are required to be supplemented to convert water in the mother liquor into glacial acetic acid so that the chemical reaction is carried out in the positive reaction direction, then oxygen is used for oxidation reaction, and if a plurality of batches of tar are accumulated more, the catalyst is poisoned and only can be distilled; the solid mixture obtained by distillation contains decarboxylation products, ring breaking products, a small amount of raw material 1-methyl-4-naphthoic acid, intermediate product 1-carboxyl-4-naphthaldehyde, intermediate product 1-carboxyl-4-naphthal methanol, product 1, 4-naphthalenedicarboxylic acid and tar generated in the oxidation of oxygen, and the conventional general treatment is to sell the solid mixture as solid waste to a qualified solid waste treatment unit, wherein 4800 yuan is paid per ton. How to remove decarboxylation, ring breaking substances and tar in solid wastes and simultaneously remove a small amount of unreacted raw materials, change an intermediate product 1-carboxyl-4-naphthalene methanol into 1, 4-naphthalene dicarboxylic acid, change an intermediate product 1-carboxyl-4-naphthalene formaldehyde into 1, 4-naphthalene dicarboxylic acid, simultaneously take out the 1, 4-naphthalene dicarboxylic acid in a solid mixture, and separate and purify the 1, 4-naphthalene dicarboxylic acid consistent with the original product from the solid mixture becomes a 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-naphthalenedicarboxylic acid from distillation residues of 1, 4-naphthalenedicarboxylic acid reaction mother liquor, which makes full use of the mother liquor for preparing the 1, 4-naphthalenedicarboxylic acid in the prior art, recovers and obtains the 1, 4-naphthalenedicarboxylic acid and reduces solid waste.
The purpose of the invention is realized by the following technical scheme:
a method for separating and purifying 1, 4-naphthalenedicarboxylic acid from distillation residues of reaction mother liquor of 1, 4-naphthalenedicarboxylic acid, comprising the steps of:
firstly, adding water into 1, 4-naphthalenedicarboxylic acid reaction mother liquor distillation residues, then adding alkali liquor to adjust the pH value to 12-14, heating to 45-55 ℃ to completely dissolve the residues, then adjusting the pH value of the solution to 3, obtaining solid waste after centrifugation, extracting the centrifuged solution with an organic solvent to obtain tar, adding alkali liquor into an extracted water layer to adjust the pH value to 10-12, heating to 60-70 ℃, adding a sodium hypochlorite solution, and carrying out heat preservation treatment after the addition is finished; removing redundant sodium hypochlorite, decoloring, acid precipitating, spin-drying and drying to obtain the 1, 4-naphthalenedicarboxylic acid.
Preferably, the alkali liquor is 30-32 wt% of 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 8-12 wt%, and more preferably 10 wt%.
Preferably, the volume mass ratio of the added amount of the sodium hypochlorite solution to the distillation residue of the 1, 4-naphthalenedicarboxylic acid reaction mother liquor is 2.5-2.7L/kg.
Preferably, the time of the heat preservation treatment is 1-1.5 h.
Preferably, the manner of removing the excess sodium hypochlorite is as follows: excess sodium hypochlorite was removed using a 10 wt% aqueous solution of sodium metabisulfite, using a test with potassium starch iodide paper without bluing.
Preferably, the decoloring mode is as follows: adjusting the pH value to 6.5 by using 10 wt% dilute sulfuric acid, adding activated carbon, stirring and decoloring at 75-85 ℃ for 40 minutes, and filtering to obtain a solution.
Preferably, the acidification mode is as follows: and heating the decolorized solution to 95-98 ℃, and adding 10 wt% of dilute sulfuric acid to adjust the pH to 1.
Preferably, the spin-drying and drying modes are as follows: and (3) cooling the acidified solution to 60 ℃, drying by spin, then rinsing by water until the pH value of the washing water is 5, and finally drying by spin-drying again.
The mechanism involved in the present invention:
adding water into distillation residues of 1, 4-naphthalenedicarboxylic acid reaction mother liquor, then adding alkali liquor, heating to dissolve the residues, adjusting the pH to 3, wherein the pH is 3, impurities cannot be removed if the pH is too high, and products can be separated if the pH is too low; under the pH value, decarboxylation and ring breaking products are separated, a small amount of unreacted raw material 1-methyl-4-naphthoic acid is separated out as solid, two intermediate products 1-carboxyl-4-naphthoic alcohol, 1-carboxyl-4-naphthoic aldehyde and a product 1, 4-naphthalenedicarboxylic acid are all in an aqueous solution in the form of sodium salt, centrifugal drying is carried out to obtain solid waste, the aqueous solution is used for extracting light tar (some oily substances) by using an organic solvent, an aqueous layer is added with alkaline solution to be adjusted to be alkaline, sodium hypochlorite is added to react alcoholic hydroxyl and aldehyde groups of the two intermediate products to form sodium carboxylate, and then decoloration, acidification and drying are carried out to obtain the qualified finished product 1, 4-naphthalenedicarboxylic acid.
Compared with the prior art, the invention has the beneficial effects that:
the invention designs a set of method for recovering 1, 4-naphthalenedicarboxylic acid from the residue aiming at the distillation residue of the 1, 4-naphthalenedicarboxylic acid reaction mother liquor, and the recovery method has simple process and easy operation and accords with the concept of green and environmental protection at the present stage. By using the method of the invention, the content of the recovered product reaches up to 99.3 percent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The liquid alkali described in the examples is a 30% strength by weight sodium hydroxide solution.
Example 1
A method for separating and purifying 1, 4-naphthalenedicarboxylic acid from distillation residues of 1, 4-naphthalenedicarboxylic acid reaction mother liquor comprises the following steps:
adding 150kg of wet 1, 4-naphthalenedicarboxylic acid reaction mother liquor distillation residue, 1200kg of water and 180L of liquid alkali into a 2000L kettle, heating to 45 ℃ to dissolve the materials, repeatedly measuring the pH value to 14, adjusting the pH value to 3 by using 10 wt% of dilute sulfuric acid, putting the solution into a centrifuge for spin-drying to obtain a solid, wherein 50kg of the solid is solid waste, adding the mother liquor into a 3000L kettle, adding 600L of chloroform, stirring for 30 minutes, standing for 30 minutes, separating a lower chloroform layer, recovering a chloroform sleeve for the next batch, adding 150L of liquid alkali into a water layer to adjust the pH value to 10, heating to 60 ℃, dropwise adding 400L of 10 wt% of sodium hypochlorite at 60 ℃, keeping the temperature for 1 hour after dropwise adding, removing excessive sodium hypochlorite by using 10 wt% of sodium metabisulfite aqueous solution (the test is based on potassium iodide test paper for testing), adjusting the pH value to 6.5 by using 10 wt% of dilute sulfuric acid, adding 3kg of activated carbon, stirring, filtering at 75 ℃ for 40 minutes, and putting the mixture into another 3000L kettle, stirring and heating to 95 ℃, dripping 10% dilute sulfuric acid at 95 ℃ to adjust the pH value to 1, cooling to 60 ℃, drying by throwing, rinsing on a centrifuge by using water until the pH value of the washing water is 5, drying by throwing and drying to obtain 60kg of 1, 4-naphthalenedicarboxylic acid (which is consistent with the product of the original batch), wherein the appearance is white, the content is 99.3%, and the product is consistent with the product of the original batch.
Example 2
A method for separating and purifying 1, 4-naphthalenedicarboxylic acid from distillation residues of 1, 4-naphthalenedicarboxylic acid reaction mother liquor comprises the following steps:
155kg of wet 1, 4-naphthalenedicarboxylic acid reaction mother liquor distillation residue, 1210kg of water and 180L of liquid alkali are put into a 2000L kettle, the temperature is raised to 55 ℃ to dissolve the materials, the pH value is 14 after repeated measurement, the pH value is adjusted to 3 by 10 wt% of dilute sulfuric acid, the solution is put into a centrifuge to be dried to obtain solid, 52kg of the solid is solid waste, the mother liquor is put into a 3000L kettle, 600L of toluene is added, the mixture is stirred for 30 minutes, the mixture is kept stand for 30 minutes, a lower toluene layer is separated, toluene is recovered and used for the next batch, 150L of liquid alkali is added into a water layer to adjust the pH value to 11, the temperature is raised to 70 ℃, 402L of 10 wt% of sodium hypochlorite is added dropwise at 70 ℃, the temperature is kept for 1 hour after the addition, the excessive sodium hypochlorite is removed by 10 wt% of sodium metabisulfite aqueous solution (the test is based on potassium iodide test paper, the test potassium iodide paper does not change in blue), the pH value is adjusted to 6.5 by 10 wt% of dilute sulfuric acid, 3kg of activated carbon is added, the activated carbon and the activated carbon is stirred at 85 ℃ and is filtered into another 3000L kettle after 40 minutes, stirring and heating to 98 ℃, dripping 10% dilute sulfuric acid at 98 ℃ to adjust the pH value to 1, cooling to 60 ℃, drying by throwing, rinsing on a centrifuge by using water until the pH value of the washing water is 5, drying by throwing and drying to obtain 62.5kg of 1, 4-naphthalenedicarboxylic acid (which is consistent with the product of the original batch) with white appearance and 99.0% of content, which is consistent with the product of the original batch.
Example, 3
A method for separating and purifying 1, 4-naphthalenedicarboxylic acid from distillation residues of 1, 4-naphthalenedicarboxylic acid reaction mother liquor comprises the following steps:
adding 148kg of wet 1, 4-naphthalenedicarboxylic acid reaction mother liquor distillation residue, 1200kg of water and 180L of liquid alkali into a 2000L kettle, heating to 50 ℃ to dissolve the materials, repeatedly measuring the pH value to be 14, adjusting the pH value to be 3 by using 10 wt% of dilute sulfuric acid, putting the mixture into a centrifuge for spin-drying to obtain solid, wherein 49kg of the solid is solid waste, adding the mother liquor into a 3000L kettle, adding 580L of 1 and 2-dichloroethane, stirring for 30 minutes, standing for 30 minutes, separating out a lower layer 1, 2-dichloroethane layer, recovering 1, 2-dichloroethane for the next batch, adding 150L of liquid alkali into a water layer to adjust the pH value to be 11, heating to 68 ℃, dropwise adding 400L of 10 wt% of sodium hypochlorite at 68 ℃, keeping the temperature for 1.5 hours after dropwise adding, removing excessive sodium hypochlorite by using 10 wt% of sodium metabisulfite aqueous solution (the test is based on potassium iodide test paper), adjusting the pH value to be 6.5 by using 10 wt% 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 ℃, dropwise adding 10% dilute sulfuric acid at 98 ℃ to adjust the pH to 1, cooling to 60 ℃, drying by throwing, rinsing on a centrifuge by using water until the pH of the rinsing water is 5, drying by throwing, and obtaining 57.3kg of 1, 4-naphthalenedicarboxylic acid (which is consistent with the product of the original batch), wherein the appearance is white, the content is 99.2%, and the product is consistent with the product of the original batch.
Example 4
A method for separating and purifying 1, 4-naphthalenedicarboxylic acid from distillation residues of 1, 4-naphthalenedicarboxylic acid reaction mother liquor comprises the following steps:
adding 152kg of wet 1, 4-naphthalenedicarboxylic acid reaction mother liquor distillation residue, 1200kg of water and 183L of liquid alkali into a 2000L kettle, heating to 48 ℃ to dissolve the materials, measuring the pH value again to be 14, adjusting the pH value to be 3 by using 10 wt% of dilute sulfuric acid, putting the solution into a centrifuge for spin-drying to obtain a solid, wherein 51.5kg of the solid is solid waste, adding the mother liquor into a 3000L kettle, adding 600L of toluene, stirring for 30 minutes, standing for 30 minutes, separating a toluene layer at the lower layer, recovering the toluene for the next batch, adding 150L of liquid alkali into a water layer to adjust the pH value to be 11, heating to 68 ℃, dropwise adding 402L of 10 wt% of sodium hypochlorite at 68 ℃, keeping the temperature for 1 hour after dropwise adding, removing excessive sodium hypochlorite by using 10 wt% of sodium metabisulfite aqueous solution (the test potassium iodide test paper does not change to blue), adjusting the pH value to be 6.5 by using 10 wt% of dilute sulfuric acid, adding 3.5kg of activated carbon, stirring, filtering at 85 ℃ for 40 minutes, and decoloring in another 3000L kettle, stirring and heating to 95 ℃, dripping 10% dilute sulfuric acid at 95 ℃ to adjust the pH value to 1, cooling to 60 ℃, drying by throwing, rinsing on a centrifuge by using water until the pH value of the washing water is 5, drying by throwing and drying to obtain 60.8kg of 1, 4-naphthalenedicarboxylic acid (which is consistent with the product of the original batch), wherein the appearance is white, the content is 99.0%, and the product is consistent with the product of the original batch.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A method for separating and purifying 1, 4-naphthalenedicarboxylic acid from distillation residues of reaction mother liquor of 1, 4-naphthalenedicarboxylic acid, which is characterized by comprising the following steps:
firstly, adding water into 1, 4-naphthalenedicarboxylic acid reaction mother liquor distillation residues, then adding alkali liquor to adjust the pH value to 12-14, heating to 45-55 ℃ to completely dissolve the residues, then adjusting the pH value of the solution to 3, centrifuging, obtaining solid waste after centrifuging, extracting the centrifuged solution with an organic solvent to obtain tar, adding alkali liquor into an extracted water layer to adjust the pH value to 10-12, heating to 60-70 ℃, adding a sodium hypochlorite solution, and carrying out heat preservation treatment after the addition is finished; removing redundant sodium hypochlorite, decoloring, acid precipitating, spin-drying and drying to obtain the 1, 4-naphthalenedicarboxylic acid.
2. The method for separating and purifying 1, 4-naphthalenedicarboxylic acid from the distillation residue of the 1, 4-naphthalenedicarboxylic acid reaction mother liquor as claimed in claim 1, wherein the volume-to-mass ratio of the amount of the sodium hypochlorite solution added to the distillation residue of the 1, 4-naphthalenedicarboxylic acid reaction mother liquor is 2.5 to 2.7L/kg.
3. The method for separating and purifying 1, 4-naphthalenedicarboxylic acid from the distillation residue of the reaction mother liquor of 1, 4-naphthalenedicarboxylic acid as claimed in any one of claims 1 to 2, characterized in that the alkali solution is 30 to 32% by weight sodium hydroxide solution.
4. The method for separating and purifying 1, 4-naphthalenedicarboxylic acid from the distillation residue of the reaction mother liquor of 1, 4-naphthalenedicarboxylic acid as claimed in claim 3, wherein the concentration of said sodium hypochlorite solution is 8 to 12% by weight.
5. The method for separating and purifying 1, 4-naphthalenedicarboxylic acid from the distillation residue of the reaction mother liquor of 1, 4-naphthalenedicarboxylic acid as claimed in any one of claims 1 to 2, wherein the heat-retaining treatment is carried out for 1 to 1.5 hours.
6. The method for separating and purifying 1, 4-naphthalenedicarboxylic acid from the distillation residue of the reaction mother liquor of 1, 4-naphthalenedicarboxylic acid as claimed in claim 5, wherein said organic solvent is at least one of chloroform, toluene and 1, 2-dichloroethane.
7. The method for separating and purifying 1, 4-naphthalenedicarboxylic acid from the distillation residue of the reaction mother liquor of 1, 4-naphthalenedicarboxylic acid as claimed in any one of claims 1 to 2, wherein the excess sodium hypochlorite is removed by: excess sodium hypochlorite was removed using a 10 wt% aqueous solution of sodium metabisulfite, using a test with potassium starch iodide paper without bluing.
8. The method for separating and purifying 1, 4-naphthalenedicarboxylic acid from the distillation residue of the reaction mother liquor of 1, 4-naphthalenedicarboxylic acid as claimed in any one of claims 1 to 2, characterized in that the decoloring is performed by: adjusting the pH value to 6.5 by using 10 wt% dilute sulfuric acid, adding activated carbon, stirring and decoloring at 75-85 ℃ for 40 minutes, and filtering to obtain a solution.
9. The method for separating and purifying 1, 4-naphthalenedicarboxylic acid from the distillation residue of the reaction mother liquor of 1, 4-naphthalenedicarboxylic acid as claimed in any one of claims 1 to 2, characterized in that the acid precipitation is carried out by: and heating the decolorized solution to 95-98 ℃, and adding 10 wt% of dilute sulfuric acid to adjust the pH to 1.
10. The method for separating and purifying 1, 4-naphthalenedicarboxylic acid from the distillation residue of the reaction mother liquor of 1, 4-naphthalenedicarboxylic acid as claimed in any one of claims 1 to 2, characterized in that the manner of spin-drying and drying is as follows: and (3) cooling the acidified solution to 60 ℃, drying by spin, then rinsing by water until the pH value of the washing water is 5, and finally drying by spin-drying again.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784874A (en) * | 2022-12-09 | 2023-03-14 | 黄石市利福达医药化工有限公司 | Purification method of 4,4' -biphenyldicarboxylic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483718A (en) * | 2002-08-12 | 2004-03-24 | 株式会社日本触媒 | Procdss for preparing hydroxyaldyl (meth) acrylate |
| DE602006002123D1 (en) * | 2006-06-12 | 2008-09-18 | Hyosung Corp | An apparatus and process for recovering acetic acid and catalyst in a naphthalene-2,6-dicarboxylic acid production process |
| CN103739484A (en) * | 2013-12-31 | 2014-04-23 | 黄石市利福达医药化工有限公司 | Preparation method of 1,4-naphthalenedicarboxylic acid |
| CN111747840A (en) * | 2020-07-21 | 2020-10-09 | 黄石市利福达医药化工有限公司 | Preparation method of 1, 4-naphthalenedicarboxylic acid |
| CN113336640A (en) * | 2021-06-07 | 2021-09-03 | 黄石市利福达医药化工有限公司 | Method for reducing content of 1, 4-naphthalenedicarboxylic acid impurities |
-
2021
- 2021-11-29 CN CN202111435360.0A patent/CN114014750B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483718A (en) * | 2002-08-12 | 2004-03-24 | 株式会社日本触媒 | Procdss for preparing hydroxyaldyl (meth) acrylate |
| DE602006002123D1 (en) * | 2006-06-12 | 2008-09-18 | Hyosung Corp | An apparatus and process for recovering acetic acid and catalyst in a naphthalene-2,6-dicarboxylic acid production process |
| CN103739484A (en) * | 2013-12-31 | 2014-04-23 | 黄石市利福达医药化工有限公司 | Preparation method of 1,4-naphthalenedicarboxylic acid |
| CN111747840A (en) * | 2020-07-21 | 2020-10-09 | 黄石市利福达医药化工有限公司 | Preparation method of 1, 4-naphthalenedicarboxylic acid |
| CN113336640A (en) * | 2021-06-07 | 2021-09-03 | 黄石市利福达医药化工有限公司 | Method for reducing content of 1, 4-naphthalenedicarboxylic acid impurities |
Non-Patent Citations (1)
| Title |
|---|
| 何志荣, 张俐霞, 朱凌皓: "2, 6-萘二甲酸及其酯的制备和应用", 煤化工, no. 01, pages 51 - 56 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115784874A (en) * | 2022-12-09 | 2023-03-14 | 黄石市利福达医药化工有限公司 | Purification method of 4,4' -biphenyldicarboxylic acid |
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