CN1128134C - Process for preparing Naphthol AS products - Google Patents
Process for preparing Naphthol AS products Download PDFInfo
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- CN1128134C CN1128134C CN 99123830 CN99123830A CN1128134C CN 1128134 C CN1128134 C CN 1128134C CN 99123830 CN99123830 CN 99123830 CN 99123830 A CN99123830 A CN 99123830A CN 1128134 C CN1128134 C CN 1128134C
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- acid
- phosphorus trichloride
- aniline
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Abstract
The present invention relates to a method for preparing naphthol AS products, which comprises the processing steps of catalyst preparation, condensation, neutralization, washing, drying, etc. During catalyst preparation, 2, 3 acid, aniline and phosphorus trichloride are used according to a molar ratio of 1: (0.9 to 1.1): (0.9 to 1.1), and the volume of solvents are 1 to 1.2 times of that of the phosphorus trichloride; in the processing step of condensation, a molar ratio of the 2, 3 acid to the aniline is 1: (1.1 to 1.4), and the volume of organic solvents are 5 to 8 times of that of the phosphorus trichloride; two stages of catalyst adding and constant flow refluxing are controlled, or a control mode that a total molar ratio of the 2, 3 acid to the phosphorus trichloride is 1: (0.2 to 0.3) and a total molar ratio of the 2, 3 acid to the aniline is 1: (1.1 to 1.2) is adopted. The present invention can enhance the quality and the yield of naphthol AS products and can also reduce the discharge amount of chlorine hydride.
Description
The present invention relates to the glacial dye process for preparing Naphthol AS products.
Azoic coupling component AS begins to go into operation in China from the fifties, product is widely used as cotton fabric dyeing, stamp primer and manufacturing rapidogen dye dyestuff and pigment dyestuff, be to make dyestuff, the important coupling composition of pigment, production method still adopts catalyst preparation so far, condensation, neutralization, suction filtration, dry this classical technology, i.e. 2,3 acid and aniline and the phosphorus trichloride benzene mixed solution for preparing 1.0: 1.16: 0.40 in molar ratio, in the solvent chlorobenzene, temperature 70-130 ℃ is carried out condensation, and reaction process is emitted the hydrogen chloride gas water and absorbed, and opens manhole then and adds the soda ash neutralization, control pH value 8-9, chlorobenzene is reclaimed in distillation, adds hot water more than 90 ℃ again, carries out suction filtration, after the washing, advance the dry finished product that gets in the rake type dryer.This technology deficiency is that the condensing agent phosphorus trichloride is excessive in causing the hydrogenchloride quantity discharged big greatly, serious to equipment corrosion, operating environment is also poor, and phosphite is many in the crude product, washing water increase, labor strength is big, rake type dryer energy consumption height again, and crude product time of drying is long and product appearance is a beige, molten o'clock below 246 ℃, content has only 98%, and is second-rate, do not reach high-grade pigment dye requirement; Yield is paced up and down about 93%, and production cost is higher.
The purpose of this invention is to provide a kind of process for preparing Naphthol AS products, adopt this method can reduce the phosphorus trichloride consumption, alleviate the quantity discharged of hydrogenchloride and washing water, can make the Naphthol AS products mass yield that a raising is all arranged simultaneously.
The present invention realizes by following technical scheme, and the preparation method of this Naphthol AS products comprises preparation of catalysts, condensation, neutralization, filtering and washing, drying process, it is characterized in that:
A, catalyzer are by 2,3 acid, aniline, phosphorus trichloride preparation, and selected organic solvent is an orthodichlorobenzene, Ortho Nitro Toluene,
B, in the condensation operation, 2,3 acid divide two sections controls with aniline in organic solvent, first section for adding catalyzer, second section is the constant temperature backflow.
During described catalyst preparation, 2,3 acid, aniline, phosphorus trichloride 1: 0.9 in molar ratio～1.1: 0.9～1.1, solvent are 1.0～1.2 times of phosphorus trichloride volume, and temperature is 30～60 ℃.In the described condensation operation, 2,3 acid are 1: 1.1～1.4 with the mol ratio of aniline, and organic flux is 5-8 a times of phosphorus trichloride.It is catalyzer to be added wherein with 1.5-3 hour at 80 ℃-135 ℃ that the branch of condensation is controlled to be first section for two sections; Second section is 135-144 ℃ of constant temperature backflow 5-10 hour.2,3 acid are 1: 0.2～0.3,2 with the total mol ratio of phosphorus trichloride, and 3 acid are 1: 1.1～1.2 with total mol ratio of aniline.Neutralization is 7-9 with its PH of 20-35% liquid caustic soda.Way be earlier in reactor with a part 2,3 acid and aniline, in organic solvent, be mixed with catalyzer with less phosphorus trichloride, in the scale tank of packing into.When the condensation operation again with major part 2,3 acid are stirred intensification with aniline in organic solvent, from scale tank, drip the catalyzer for preparing, the insulation reaction in 8-10 hour that at high temperature refluxes finishes and adds the liquid caustic soda neutralization, then the organic solvent distillation is reclaimed, add after hot water stirs for some time, the filter cake of carry out suction filtration, wash, draining advances that drying goes out finished product in the flash distillation dryer.The organic solvent of selecting for use is an orthodichlorobenzene, Ortho Nitro Toluene etc.In process of the test, find the quality of product, yield and preparation of catalysts quality, rate of addition, the condensation controlled temperature, in the time pH value adjusting and drying relevant.
The process that realizes this invention is such: in the reactor of agitator is housed with 2,3 acid, aniline, phosphorus trichloride 1: 0.9 in molar ratio～1.1: 0.9～1.1 drops in solvent orthodichlorobenzene or the Ortho Nitro Toluene, in temperature is between 30～60 ℃, mix and stirred 1-3 hour, the volume ratio of solvent and phosphorus trichloride be 1.0～1.2: 1.0 leave standstill 1 hour then after, in the scale tank of packing into; During condensation, first section in the reactor that stirring and backflow gas-liquid condensation separator are housed, 2,3 acid drop in the organic solvent with aniline 1: 1.1 in molar ratio～1.4, the volume ratio of organic solvent and phosphorus trichloride is 5～8: 1 mixes half an hour, be warmed up to 80 ℃ with nearly 1 hour, progressively add wherein with 1.5～3 hours catalyzer then preparation, after making temperature rise to 135 ℃ from 80 ℃ reposefully, stablized 1 hour at 135 ℃, second section is to reflux 5～10 hours at 135～144 ℃ of constant temperature then, uses CO again
2Or N
2Air pressure is gone in the reactor of belt stirrer and condenser, neutralizes, and in 1～3 hour pH value is transferred to 7-9 with 20～35% liquid caustic soda, with directly and indirect steam heat simultaneously, steam organic solvent after; Add hot water more than 95 ℃, stir after 1 hour, carry out suction filtration, wash, drain.During drying process, water content less than 20% filter cake, is entered the flash distillation dryer drying, 110～200 ℃ of temperature controls, the elapsed time got qualified finished product less than 30 minutes to material therein.
The technical program can realize like this that also promptly total mol ratio of 2,3 acid and phosphorus trichloride is 1: 0.2～0.3,2, and total mol ratio of 3 acid and aniline is 1: 1.10～1.20, and all the other processes are with above-mentioned the same.
After implementing technique scheme, the present invention compares with traditional technology, has the following advantages.
(1) adopt raw catalyst after, can reduce by 25～50% phosphorus trichloride consumptions, and then can reduce hydrogen chloride gas about 50%, to prolonging in work-ing life of equipment, improve workman's operating environment.
(2) because the consumption of phosphorus trichloride reduces, and phosphite content reduces, washing water can reduce closely half, have saved the energy, have alleviated labor strength and environmental improvement pressure.
(3) adopt liquid caustic soda with operation in, neutralization is carried out in sealed vessel, save human and material resources, operate comfortable, convenience, environment is good.
(4) eliminated the high heavy rake type dryer of energy consumption, used flash distillation instead and not only reduced requirement equipment, easy to use, reduce the operation field dust to fly upward maintenance cost also low, and can improve the product appearance quality.
(5) outward appearance of product can reach canescence, obviously is better than beige, and fusing point can reach more than 247.5 ℃, and content can reach high-grade dyestuff, pigment mass requirement more than 99.0%, can significantly improve its quality competition power.
(6) yield of product is more than 97%, improved nearly 4 percentage points than 93%, and production cost obviously reduces.
Now, enforcement of the present invention is further described in conjunction with technique scheme.
Example 1, in the reactor of stirring is housed with 229.5 part 2,3 acid, 252 parts of aniline, 206.5 part phosphorus trichloride drops in the solvent orthodichlorobenzene, the added volume of orthodichlorobenzene is 1.1 times of phosphorus trichloride volume, controlled temperature stirs after 2 hours for 40 ℃, left standstill 1 hour, with pump with joining catalyzer move in the scale tank, in the reactor that stirring and backflow gas-liquid condensation separator are housed, with 2640 part 2,3 acid, 2904 parts of aniline are put in the orthodichlorobenzene, and organic solvent is 7 times of the volumes of used phosphorus trichloride, mixes half an hour, be warmed up to 80 ℃ with 1 hour again, with 3 hours the catalyzer for preparing is dripped wherein then, temperature slowly is raised to 132 ℃, stablizes 1 hour at 135 ℃, after 142 ℃ of constant temperature refluxed 9.5 hours, use N then
2Be pressed in the reactor of band stirring and condenser, is 8.0 (on-the-spot precision and the extensive test paper used is in conjunction with measuring) with 30% liquid caustic soda at 2 hours adjustment pH values, open again directly and indirect steam begins to heat simultaneously, reclaim orthodichlorobenzene, after recovery finishes, add that hot water stirred 1 hour for 280 parts more than 95 ℃, put into suction filtration groove suction filtration while hot, be divided into four parts with 280 parts again, wash four times, drain to filter cake moisture content less than 15%, then filter cake is put into temperature in 120-150 ℃ flash distillation dryer, the beginning discharging gets 2783.5 parts of yields 97% of dry product after 10 minutes, and product appearance is a canescence, fusing point reaches 248.0 ℃, content 99.1%.
Example 2, in the reactor of agitator is housed with 229.5 part 2,3 acid, 252 parts of aniline, 206.5 part phosphorus trichloride, drop in the solvent Ortho Nitro Toluene, the added volume of Ortho Nitro Toluene is 1.2 times of phosphorus trichloride volume, 45 ℃ of controlled temperature, stir and left standstill 1 hour after 3 hours, with pump with joining catalyzer move in the scale tank, in the reactor that stirring and backflow gas-liquid condensation separator are housed, with 2640 part of 2,3 acid, 2904 parts of aniline drop in the Ortho Nitro Toluene, Ortho Nitro Toluene is 8 times of the volumes of used phosphorus trichloride, mixes half an hour, with 45 minutes temperature is raised to 80 ℃ again and with 3 hours the catalyzer for preparing is dripped wherein then, temperature is raised to 134 ℃, stablized 1 hour at 135 ℃, after 144 ℃ of constant temperature refluxed 10 hours, use N then
2Be pressed in the reactor of band stirring and condenser, adjusting PH with 25% liquid caustic soda at 1.5 hours is 7.5, open again directly and indirect steam begins heating, recovery Ortho Nitro Toluene simultaneously, the recovery solvent finishes, add that water stirred 1 hour for 290 parts more than 95 ℃, put into suction filtration groove suction filtration while hot, again 300 parts of hot water are divided four washings, drain to cake moisture be 12%; Then filter cake is put into temperature in 110-150 ℃ flash distillation dryer after 6 minutes the beginning discharging get 2811 parts of dry products, yield 98.0%, product appearance light gray-white, fusing point reach 248.2 ℃, content 99.3%.
Claims (5)
1, a kind of process for preparing Naphthol AS products comprises preparation of catalysts, condensation, neutralization, filtering and washing, drying process, it is characterized in that:
A, catalyzer are by 2,3 acid, aniline, phosphorus trichloride preparation, and selected organic solvent is an orthodichlorobenzene, Ortho Nitro Toluene,
B, in the condensation operation, 2,3 acid divide two sections controls with aniline in organic solvent, first section for adding catalyzer, second section is the constant temperature backflow;
During described catalyst preparation, 2,3 acid, aniline, phosphorus trichloride 1: 0.9 in molar ratio～11: 0.9～1.1,
Solvent is 1.0～1.2 times of phosphorus trichloride volume, and temperature is 30～60 ℃;
In described condensation operation, 2,3 acid are 1: 1.1～1.4 with the mol ratio of aniline, and organic solvent is 5-8 a times of phosphorus trichloride.
2, a kind of process for preparing Naphthol AS products comprises preparation of catalysts, condensation, neutralization, filtering and washing, drying process, it is characterized in that:
A, catalyzer are by 2,3 acid, aniline, phosphorus trichloride preparation, and selected organic solvent is an orthodichlorobenzene, Ortho Nitro Toluene,
B, in the condensation operation, 2,3 acid divide two sections controls with aniline in organic solvent, first section for adding catalyzer, second section is the constant temperature backflow;
During described catalyst preparation, 2,3 acid are 1: 0.2～0.3,2 with the total mol ratio of phosphorus trichloride, and 3 acid are 1: 1.1～1.2 with total mol ratios of aniline; Solvent is 1.0～1.2 times of phosphorus trichloride volume, and temperature is 30～60 ℃;
In described condensation operation, organic solvent is 5-8 a times of phosphorus trichloride.
3, process for preparing Naphthol AS products according to claim 1 and 2 is characterized in that: it is catalyzer to be added wherein with 1.5-3 hour at 80 ℃-135 ℃ that the branch of described condensation is controlled to be first section for two sections; Second section is 135-144 ℃ of constant temperature backflow 5-10 hour.
4, process for preparing Naphthol AS products according to claim 1 and 2 is characterized in that: neutralization is 7-9 with its PH of 20-35% liquid caustic soda.
5, process for preparing Naphthol AS products according to claim 1 and 2 is characterized in that: when carrying out expansion drying cake moisture less than 20%, 110-200 ℃ of temperature control, material therein the elapsed time less than 30 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123830 CN1128134C (en) | 1999-11-15 | 1999-11-15 | Process for preparing Naphthol AS products |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123830 CN1128134C (en) | 1999-11-15 | 1999-11-15 | Process for preparing Naphthol AS products |
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| CN1251834A CN1251834A (en) | 2000-05-03 |
| CN1128134C true CN1128134C (en) | 2003-11-19 |
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| CN 99123830 Expired - Fee Related CN1128134C (en) | 1999-11-15 | 1999-11-15 | Process for preparing Naphthol AS products |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838244B (en) * | 2010-06-03 | 2012-11-21 | 山东金城医药化工股份有限公司 | Organic solvent synthetic method of azoic coupling component ASBI |
| CN102532035B (en) * | 2011-12-30 | 2014-01-15 | 郭祥荣 | Method for synthesizing azoic coupling component AS-BI |
| CN104447392B (en) * | 2014-11-28 | 2016-06-15 | 济宁阳光化学有限公司 | A kind of preparation method of azoic coupling component AS |
| CN105906527A (en) * | 2015-09-15 | 2016-08-31 | 雷玉金 | Naphthol AS mother liquor recovery method |
| CN106316874A (en) * | 2016-08-23 | 2017-01-11 | 山东阳光颜料有限公司 | Method for preparing azoic coupling component AS-D |
| CN111808434B (en) * | 2020-07-20 | 2021-07-02 | 青岛科技大学 | Method for preparing naphthol AS series azo dye |
| CN112023957A (en) * | 2020-09-24 | 2020-12-04 | 青岛科技大学 | B-P-O group-based catalyst and method for preparing naphthol by using same |
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