CN114479507A - Preparation method of environment-friendly disperse violet 26 - Google Patents
Preparation method of environment-friendly disperse violet 26 Download PDFInfo
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- CN114479507A CN114479507A CN202210120946.6A CN202210120946A CN114479507A CN 114479507 A CN114479507 A CN 114479507A CN 202210120946 A CN202210120946 A CN 202210120946A CN 114479507 A CN114479507 A CN 114479507A
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- GTZCVFVGUGFEME-UHFFFAOYSA-N aconitic acid Chemical compound OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002351 wastewater Substances 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000003916 acid precipitation Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000001103 potassium chloride Substances 0.000 claims abstract description 7
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 7
- 238000009833 condensation Methods 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 6
- 238000005204 segregation Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 28
- KZYAYVSWIPZDKL-UHFFFAOYSA-N 1,4-diamino-2,3-dichloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=C(Cl)C(Cl)=C2N KZYAYVSWIPZDKL-UHFFFAOYSA-N 0.000 claims description 22
- 239000012452 mother liquor Substances 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- 238000007599 discharging Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical group [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 12
- 239000008234 soft water Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 238000002955 isolation Methods 0.000 claims description 5
- 230000020477 pH reduction Effects 0.000 claims description 5
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000003350 kerosene Substances 0.000 claims description 4
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- KSSNXJHPEFVKHY-UHFFFAOYSA-N phenol;hydrate Chemical compound O.OC1=CC=CC=C1 KSSNXJHPEFVKHY-UHFFFAOYSA-N 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 159000000000 sodium salts Chemical class 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000011084 recovery Methods 0.000 description 10
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000975 dye Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- -1 1, 4-dinitro-2, 3-dichloroanthraquinone Chemical compound 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- QLYNDPSMXHPWNH-UHFFFAOYSA-N 2,3-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=C(N)C(N)=C2 QLYNDPSMXHPWNH-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NZTGGRGGJFCKGG-UHFFFAOYSA-N 1,4-diamino-2,3-diphenoxyanthracene-9,10-dione Chemical compound C=1C=CC=CC=1OC1=C(N)C=2C(=O)C3=CC=CC=C3C(=O)C=2C(N)=C1OC1=CC=CC=C1 NZTGGRGGJFCKGG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920004933 Terylene® Polymers 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 1
- 239000000992 solvent dye Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/54—Amino-hydroxy-anthraquinones; Ethers and esters thereof etherified
- C09B1/547—Anthraquinones with aromatic ether groups
Abstract
The invention discloses a preparation method of environment-friendly disperse violet 26, which comprises the steps of condensation, vacuum dephenolization, segregation, filtration, oxidation, acid precipitation, wastewater treatment and the like, wherein sodium salt and potassium salt in the reaction are fully separated, so that the product yield is improved; the recycling of sylvite in the wastewater is realized for the first time, and the discharge of the saliferous wastewater is reduced; and the key raw material phenol is recycled, so that the production cost is greatly reduced. The preparation process is environment-friendly and efficient, ensures the yield and purity of the product, and is more favorable for industrial production of disperse violet 26.
Description
Technical Field
The invention belongs to the technical field of dye synthesis, and particularly relates to a preparation method of environment-friendly disperse violet 26.
Background
The disperse violet 26 has a chemical name of 1, 4-diamino-2, 3-diphenoxyanthraquinone, and a structural formula shown in formula I, and is an important anthraquinone disperse dye. It is mainly used for dyeing terylene and blended fabrics thereof, and can also be used as solvent dye and for coloring plastics and polyester. Disperse violet 26 has a bright color and excellent color fastness, and thus is widely used in the field of dyes.
Patent CN108659567A discloses a synthesis process of disperse violet 26, which specifically comprises the steps of carrying out condensation reaction on 1, 4-dinitro-2, 3-dichloroanthraquinone and sodium phenolate in the presence of an organic solvent o-dichlorobenzene to generate 1, 4-dinitro-2, 3-diphenoxy anthraquinone, and then carrying out reduction reaction in the presence of alumina and a solvent methanol to generate a target product. The method can not realize one-step reaction to prepare products, and has a complex route; in the production process, a high-pressure kettle is required and hydrogen is introduced, so that the requirement on equipment is high; the method needs a metal catalyst of alumina, is difficult to recover, has poor environmental protection, and is not suitable for industrial production of the disperse violet 26.
Patent CN111073333A discloses a preparation method of disperse violet 26, which comprises the steps of dissolving 1, 4-diamino-2, 3-dichloroanthraquinone in phenol, adding KOH for complete reaction, cooling to separate out disperse violet 26, and continuously cooling and recrystallizing with methanol to obtain a target product. The method has the disadvantages that a large amount of phenol is needed, and sylvite generated by the reaction cannot be recycled and treated, so that the method is poor in environmental friendliness; meanwhile, the yield of the process is unstable, the average yield is only about 80%, and the large-scale production of disperse violet 26 is limited.
Today, the environmental protection awareness of people is gradually enhanced, a green and clean production process is particularly important, but the current production process for preparing the key dye disperse violet 26 generates a large amount of wastewater, and the mixture in the wastewater is difficult to separate, and if the wastewater is directly treated and is not recycled, a large amount of waste is inevitably caused.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the preparation method of the environment-friendly disperse violet 26, which improves the environmental protection property and the waste utilization rate of the production process and ensures that the product has higher yield and purity.
The technical scheme for solving the technical problems is as follows:
the invention provides a preparation method of environment-friendly disperse violet 26, which is characterized by comprising the following steps:
(1) condensation: adding 2, 3-dichloro-1, 4-diaminoanthraquinone, phenol, an inert solvent and an acid-binding agent into a reaction kettle, and collecting distillate after complete reaction;
(2) vacuum dephenolization: carrying out vacuum distillation on the reaction liquid and the distillate in the step (1), and stopping after distilling 30-40% of the total amount;
(3) isolation: pouring the liquid distilled in the step (2) into a segregation kettle, cooling, and sequentially adding liquid caustic soda and soft water; continuing stirring to separate disperse violet 26 from phenol;
(4) and (3) filtering: after the separation is finished, filtering and washing the materials, and simultaneously extracting and discharging mother liquor to an acid separation kettle; washing materials with hot water, discharging the washing material liquid in the early stage into an acid precipitation kettle, and discharging the washing material liquid in the later stage into phenol water for treatment until the pH value of the materials is 7-9, and discharging;
(5) and (3) oxidation: oxidizing the material obtained in the step (4) by using an oxidant alkaline water and/or sodium hypochlorite;
(6) acid precipitation: adding acid to maintain the pH value in the acid precipitation kettle to be 6.0-7.0; conveying the materials in the acidification kettle to a settling tank for standing, separating a water layer to a wastewater tank, and transferring the phenol mother liquor to a neutralization kettle; adjusting the pH value of the phenol mother liquor to be 6.0-7.0, and then conveying the phenol mother liquor to a rectifying still for rectification;
(7) wastewater treatment: adjusting the pH value of the wastewater in the wastewater tank in the step (6) to 6.5-7.0 by using hydrochloric acid, extracting by using an extraction solvent, and layering; distilling the solvent layer to recover the solvent, phenol and sylvite; biochemical treatment of the water layer;
further, the inert solvent in the step (1) is a solvent which has a boiling point between 120 ℃ and 175 ℃ and is not soluble in water, preferably phenol; the acid-binding agent is potassium carbonate; the feeding weight ratio of the inert solvent, the phenol, the 2, 3-dichloro-1, 4-diaminoanthraquinone and the acid-binding agent is 1.5-2.5: 2.5-3: 0.9-1.1: 0.6-0.8, preferably 1.5:3:0.9: 0.6;
further, the mass of the distillate in the step (1) is 1/10-1/5 of the addition amount of 2, 3-dichloro-1, 4-diaminoanthraquinone;
further, the reaction temperature of the step (1) is 195-200 ℃, and the reaction time is 2-4 h;
further, the vacuum degree in the step (2) is gradually increased, and the distillation temperature is 150-160 ℃;
further, the distilled liquid in the step (2) contains 50-70% of phenol by volume, and the balance is water;
further, in the step (3), the liquid alkali is a 40% sodium hydroxide solution, and the mass ratio of the liquid alkali to the 2, 3-dichloro-1, 4-diaminoanthraquinone is 0.5-0.6: 1; the mass ratio of the soft water to the 2, 3-dichloro-1, 4-diaminoanthraquinone is 1.5-1.7: 1;
further, the material washing in the step (4) adopts hot water with the temperature of more than 80 ℃, and the material is washed for the first 5-6 times to obtain a material washing liquid in the early stage;
further, the dosage of the oxidant in the step (5) is consistent with that of the liquid alkali in the step (3) in kg; the oxidant is preferably 40% sodium hydroxide solution;
further, the acid in the step (6) is hydrochloric acid and/or sulfuric acid; the standing time is more than 6 hours;
further, the extraction solvent in the step (7) is one or more of benzene, kerosene, xylene or dichloroethane; the volume of the extraction solvent is 8-10% of the volume of the wastewater;
in the step (7), the water layer contains phenol of 800ppm or less, has a COD of 400 to 450, and has a chroma of 4 to 8.
The invention has the beneficial effects that:
the invention provides a comprehensive environment-friendly disperse violet 26 preparation method comprising the steps of condensation, vacuum dephenolization, segregation, filtration, oxidation, acidification and wastewater treatment, and compared with the prior art, the method uses liquid alkali with proper concentration and dosage to fully separate sodium salt and potassium salt in the reaction, thereby improving the product yield; the recycling of sylvite in the wastewater is realized for the first time, and the discharge of the saliferous wastewater is reduced; meanwhile, the recycling of the key raw material phenol is realized by designing a vacuum distillation procedure, so that the production cost is greatly reduced, the method is more environment-friendly and efficient, the yield and the purity of the product are ensured, and the industrial production of disperse violet 26 is facilitated.
Drawings
FIG. 1: a synthetic process flow diagram of disperse violet 26.
Detailed Description
The invention is illustrated but not limited by the following examples. The technical solutions protected by the present invention are all the simple replacements or modifications made by the skilled person in the art.
Example 1:
(1) condensation: adding 2, 3-dichloro-1, 4-diaminoanthraquinone, phenol, chlorobenzene and acid-binding agent potassium carbonate into a reaction kettle, wherein the feeding weight ratio of the chlorobenzene to the phenol to the 2, 3-dichloro-1, 4-diaminoanthraquinone to the potassium carbonate is 1.5:3:0.9:0.6, the feeding amount of the 2, 3-diaminoanthraquinone is 300kg, stirring uniformly, gradually heating to 200 ℃, keeping the temperature for reaction for 2 hours, and generating CO2Discharging, and collecting the liquid distilled in the reaction to obtain distillate; the mass of the distillate is 0.1 time of the addition mass of the 2, 3-dichloro-1, 4-diaminoanthraquinone;
(2) vacuum dephenolization: vacuum distilling the reaction liquid and the distillate obtained in the step (1) at 160 ℃ under a distiller, wherein the vacuum degree is gradually increased from small to small so as to recover part of excessive phenol, and the distillation is stopped after 30 percent of the total amount is distilled out, wherein the content of phenol in the distillate is 50 percent by volume, and the balance is water;
(3) isolation: pouring the distilled liquid into a separation kettle, reducing the temperature to 130 ℃, adding liquid alkali, wherein the addition amount of the liquid alkali is 0.6 times of the mass of the 2, 3-dichloro-1, 4-diaminoanthraquinone, the liquid alkali is a 40% sodium hydroxide solution, adding soft water into the separation kettle after the addition of the alkali is finished, the addition amount of the soft water is 1.6 times of the mass of the 2, 3-dichloro-1, 4-diaminoanthraquinone, and controlling the temperature at 85 ℃ during the addition of the soft water; after the soft water addition is completed, stirring is continued for more than 30min, and the temperature in the kettle is kept at more than 80 ℃ to separate disperse violet 26 from phenol.
(4) And (3) filtering: after stirring, opening a bottom valve of the separation kettle, and conveying the materials to a filter tank by a pump for filtering and washing; when the filter tank is fed, starting a vacuum pump to extract mother liquor and discharging the mother liquor into an acid precipitation kettle; after mother liquor is pumped to dryness, washing the material with hot water of more than 80 ℃, and discharging the washing water into an acid precipitation kettle for the first 6 times; discharging the later washing water to phenol water for treatment until the pH value of the material is 8, and discharging;
(5) and (3) oxidation: adding 40% sodium hydroxide solution for oxidation, wherein the amount of the sodium hydroxide solution is consistent with that of the liquid caustic soda in the step (3);
(6) acid precipitation: the mother liquor and the early-stage washing liquid are combined into an acid separation kettle, and hydrochloric acid is slowly added into the acid separation kettle until the pH value is 7.0 and is stable; conveying all the materials in the acidification kettle to a settling tank by using a pump, standing for more than 6 hours, separating a water layer to a wastewater tank, and transferring the phenol mother liquor to a neutralization kettle; adjusting the pH value of the phenol mother liquor to 7.0, and then conveying the phenol mother liquor to a rectifying still for rectification;
(7) wastewater treatment: adjusting the pH value of the wastewater in the wastewater tank in the step (6) to 6.5 by hydrochloric acid, adding kerosene, stirring, extracting, standing and layering, wherein the adding volume of an extraction solvent is 8% of the amount of the wastewater; after layering, discharging the lower water layer with clear layering into a biochemical treatment tank of a wastewater station for treatment, wherein the lower water layer contains less than 800ppm of phenol, has COD (chemical oxygen demand) of 450 and has the chroma of 6; pumping the upper solvent layer into a distillation still, and recovering the solvent, phenol and sylvite.
By the method of example 1, the yield of disperse violet 26 was 93.4%, the recovery rate of potassium salt was 90%, and the recovery rate of phenol was 98%.
Example 2:
(1) condensation: adding 2, 3-dichloro-1, 4-diaminoanthraquinone, phenol, chlorobenzene and acid-binding agent potassium carbonate into a reaction kettle, wherein the feeding weight ratio of the chlorobenzene to the phenol to the 2, 3-dichloro-1, 4-diaminoanthraquinone to the potassium carbonate is 1.5:3:0.9:0.6, the feeding amount of the 2, 3-diaminoanthraquinone is 300kg, stirring uniformly, gradually heating to 200 ℃, keeping the temperature for reaction for 2 hours, and generating CO2Discharging, and collecting the liquid distilled in the reaction to obtain distillate; the mass of the distillate is 0.1 time of the addition mass of the 2, 3-dichloro-1, 4-diaminoanthraquinone;
(2) vacuum dephenolization: vacuum distilling the reaction liquid and the distillate obtained in the step (1) at 160 ℃ under a distiller, wherein the vacuum degree is gradually increased from small to small so as to recover part of excessive phenol, and the distillation is stopped after 30 percent of the total amount is distilled out, wherein the content of phenol in the distillate is 50 percent by volume, and the balance is water;
(3) isolation: pouring the distilled liquid into a separation kettle, reducing the temperature to 130 ℃, adding liquid alkali, wherein the addition amount of the liquid alkali is 0.5 times of the mass of the 2, 3-dichloro-1, 4-diaminoanthraquinone, the liquid alkali is a 40% sodium hydroxide solution, adding soft water into the separation kettle after the addition of the alkali is finished, the addition amount of the soft water is 1.6 times of the mass of the 2, 3-dichloro-1, 4-diaminoanthraquinone, and controlling the temperature at 85 ℃ during the addition of the soft water; after the soft water addition is completed, stirring is continued for more than 30min, and the temperature in the kettle is kept at more than 80 ℃ to separate disperse violet 26 from phenol.
(4) And (3) filtering: after stirring, opening a bottom valve of the separation kettle, and conveying the materials to a filter tank by a pump for filtering and washing; when the filter tank is fed, starting a vacuum pump to extract mother liquor and discharging the mother liquor into an acid precipitation kettle; after mother liquor is pumped to dryness, washing the material with hot water of more than 80 ℃, and discharging the washing water into an acid precipitation kettle for the first 6 times; discharging the later washing water to phenol water for treatment until the pH value of the material is 8, and discharging;
(5) and (3) oxidation: adding sodium hypochlorite for oxidation, wherein the amount of the sodium hypochlorite is consistent with that of the caustic soda liquid in the step (3);
(6) acid precipitation: the mother liquor and the early-stage washing liquid are combined into an acid separation kettle, and hydrochloric acid is slowly added into the acid separation kettle until the pH value is 7.0 and is stable; conveying all the materials in the acidification kettle to a settling tank by using a pump, standing for more than 6 hours, separating a water layer to a wastewater tank, and transferring the phenol mother liquor to a neutralization kettle; adjusting the pH value of the phenol mother liquor to 7.0, and then conveying the phenol mother liquor to a rectifying still for rectification;
(7) wastewater treatment: adjusting the pH value of the wastewater in the wastewater tank in the step (6) to 6.5 by hydrochloric acid, adding kerosene, stirring, extracting, standing and layering, wherein the adding volume of an extraction solvent is 8% of the amount of the wastewater; after layering, discharging the lower water layer with clear layering into a biochemical treatment tank of a wastewater station for treatment, wherein the lower water layer contains less than 800ppm of phenol, has COD (chemical oxygen demand) of 450 and has the chroma of 6; pumping the upper solvent layer into a distillation still, and recovering the solvent, phenol and sylvite.
By the method of example 2, the yield of disperse violet 26 was 92.8%, the recovery of potassium salt was 88%, and the recovery of phenol was 96%.
Comparative example 1:
the amount of the liquid alkali used in only "isolation" in this example was 0.3 times the mass of 2, 3-dichloro-1, 4-diaminoanthraquinone, and the liquid alkali was a 30% sodium hydroxide solution, and the rest was the same as in example 1.
With the preparation method of comparative example 1, the yield of disperse violet 26 was 81.8%, the recovery rate of potassium salt was 70%, and the recovery rate of phenol was 92%.
Comparative example 2:
the "vacuum dephenolation" step is not included in this example and the remainder is the same as in example 1.
By the preparation method of comparative example 2, the yield of disperse violet 26 was 92.4%, the recovery rate of potassium salt was 89%, and the recovery rate of phenol was 70%.
Comparative example 3:
the "oxidation" step is not included in this example, and the rest is the same as in example 1.
By the preparation method of comparative example 3, the yield of disperse violet 26 was 93.2%, the recovery rate of potassium salt was 74%, and the recovery rate of phenol was 94%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept of the present invention, and these changes and modifications are all within the scope of the present invention.
Claims (10)
1. The preparation method of the environment-friendly disperse violet 26 is characterized by comprising the following steps:
(1) condensation: adding 2, 3-dichloro-1, 4-diaminoanthraquinone, phenol, an inert solvent and an acid-binding agent into a reaction kettle, and collecting distillate after complete reaction;
(2) vacuum dephenolization: carrying out vacuum distillation on the reaction liquid and the distillate in the step (1), and stopping after distilling 30-40% of the total amount;
(3) isolation: pouring the liquid distilled in the step (2) into a segregation kettle, cooling, and sequentially adding liquid caustic soda and soft water; continuing stirring to separate disperse violet 26 from phenol;
(4) and (3) filtering: after the separation is finished, filtering and washing the materials, and simultaneously extracting and discharging mother liquor to an acid separation kettle; washing materials with hot water, discharging the washing material liquid in the early stage into an acid precipitation kettle, and discharging the washing material liquid in the later stage into phenol water for treatment until the pH value of the materials is 7-9, and discharging;
(5) and (3) oxidation: oxidizing the material obtained in the step (4) by using an oxidant alkaline water and/or sodium hypochlorite;
(6) acid precipitation: adding acid to maintain the pH value in the acid precipitation kettle to be 6.0-7.0; conveying the materials in the acidification kettle to a settling tank for standing, separating a water layer to a wastewater tank, and transferring the phenol mother liquor to a neutralization kettle; adjusting the pH value of the phenol mother liquor to be 6.0-7.0, and then conveying the phenol mother liquor to a rectifying still for rectification;
(7) wastewater treatment: adjusting the pH value of the wastewater in the wastewater tank in the step (6) to 6.5-7.0 by using hydrochloric acid, extracting by using an extraction solvent, and layering; distilling the solvent layer to recover the solvent, phenol and sylvite; the water layer is treated biochemically.
2. The method according to claim 1, wherein the inert solvent in the step (1) is a solvent having a boiling point of 120 to 175 ℃ and being immiscible with water; the acid-binding agent is potassium carbonate; the feeding weight ratio of the inert solvent, the phenol, the 2, 3-dichloro-1, 4-diaminoanthraquinone and the acid-binding agent is 1.5-2.5: 2.5-3: 0.9-1.1: 0.6-0.8.
3. The preparation method according to claim 1, wherein the mass of the distillate in the step (1) is 1/10-1/5 of the addition amount of 2, 3-dichloro-1, 4-diaminoanthraquinone.
4. The preparation method according to claim 1, wherein the vacuum degree in the step (2) is gradually increased, and the distillation temperature is 150-160 ℃.
5. The method according to claim 1, wherein the distilled liquid in the step (2) contains 50 to 70% by volume of phenol, and the balance is water.
6. The preparation method according to claim 1, wherein the liquid alkali in the step (3) is a 40% sodium hydroxide solution, and the mass ratio of the liquid alkali to the 2, 3-dichloro-1, 4-diaminoanthraquinone is 0.5-0.6: 1; the mass ratio of the soft water to the 2, 3-dichloro-1, 4-diaminoanthraquinone is 1.5-1.7: 1.
7. The preparation method according to claim 1, wherein hot water with the temperature of more than 80 ℃ is adopted for material washing in the step (4), and the material is washed for the first 5-6 times to obtain an early-stage material washing liquid.
8. The method according to claim 1, wherein the acid in the step (6) is hydrochloric acid and/or sulfuric acid; the standing time is more than 6 h.
9. The preparation method according to claim 1, wherein the extraction solvent in step (7) is one or more of benzene, kerosene, xylene or dichloroethane; the volume of the extraction solvent is 8-10% of the volume of the wastewater.
10. The method according to claim 1, wherein the aqueous layer in the step (7) contains phenol at 800ppm or less, has a COD of 400 to 450, and has a color of 4 to 8.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2225013A (en) * | 1937-05-11 | 1940-12-17 | Soc Of Chemical Ind | Dyestuffs of the anthraquinone series and process of making same |
| CN106893341A (en) * | 2017-03-14 | 2017-06-27 | 江苏亚邦染料股份有限公司 | The industrialized preparing process of disperse violet 26 |
| CN111073333A (en) * | 2019-12-20 | 2020-04-28 | 南京金浩医药科技有限公司 | Preparation method of disperse violet 26 |
| CN112143251A (en) * | 2020-09-17 | 2020-12-29 | 湖北彩德新材料科技有限公司 | Plastic colorant disperse violet 26 and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2225013A (en) * | 1937-05-11 | 1940-12-17 | Soc Of Chemical Ind | Dyestuffs of the anthraquinone series and process of making same |
| CN106893341A (en) * | 2017-03-14 | 2017-06-27 | 江苏亚邦染料股份有限公司 | The industrialized preparing process of disperse violet 26 |
| CN111073333A (en) * | 2019-12-20 | 2020-04-28 | 南京金浩医药科技有限公司 | Preparation method of disperse violet 26 |
| CN112143251A (en) * | 2020-09-17 | 2020-12-29 | 湖北彩德新材料科技有限公司 | Plastic colorant disperse violet 26 and preparation method thereof |
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