CN103694126A - Process for refining 1-amino-anthraquinone - Google Patents
Process for refining 1-amino-anthraquinone Download PDFInfo
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- CN103694126A CN103694126A CN201310634840.9A CN201310634840A CN103694126A CN 103694126 A CN103694126 A CN 103694126A CN 201310634840 A CN201310634840 A CN 201310634840A CN 103694126 A CN103694126 A CN 103694126A
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Abstract
The invention discloses a process for refining 1-amino-anthraquinone. The process comprises the following steps: adding a sulfonating agent into nitrified mixed nitroanthraquinone and water, performing sulfonating treatment at the PH of 8-9 and temperature of 95-100 DEG C, cooling 80 DEG C or below, filtering, washing with water and drying; adding the obtained dried product into a polar solvent, heating to 135-140 DEG C for performing primary dissolving and refining, cooling to 50 DEG C, filtering and washing by use of the polar solvent; performing secondary dissolving and refining on the washed wet product in the polar solvent, performing the similar treatment on the mother solution and washing solution; reducing by use of sodium sulfide, filtering, washing, and drying to obtain the product 1-amino-anthraquinone. According to the process, the selected sulfonating agent and polar solvent have high selective removal capacity on organic impurities such as other useless nitro by-products. Compared with the original process, the process has the advantages that the purity and yield of the obtained product are obviously improved, the operation is simple, the production is stable, and the production cost is greatly reduced. Moreover, the purity of the 1-amino-anthraquinone can be over 99.5%, the yield is improved by over 10%, waste residues are reduced, the residues are reduced by about 5%, and the purity can be up to 90-93%.
Description
Technical field
The present invention relates to a kind of 1-aminoanthraquinone refining process, belong to dyestuff intermediate preparation technology field.
Background technology
1-aminoanthraquinone, is a kind of important dyestuff intermediate, is mainly used in the production of important dye species such as disperseing, acid, active.It is to mix nitroanthraquinone dry product that former 1-aminoanthraquinone is produced process for refining, in solvent dimethyl formamide, refine to obtain 1-nitroanthraquinone, this process solvent consumption is large, reclaim the consumption energy high, and 1-nitroanthraquinone yield is on the low side, 1,5-dinitroanthraquinone is higher, causes 1-aminoanthraquinone purity on the low side, total recovery 65% left and right.
This technique is directly mixed nitroanthraquinone sulfonation pre-treatment after nitrated dilution, remove after most of by product, recycle a small amount of solvent treatment, and adopt solvent secondary to apply mechanically technique, solve the problems referred to above, when reducing production costs, also improved quality product.
Summary of the invention
The object of this invention is to provide a kind of 1-aminoanthraquinone process for refining, directly after nitrated dilution, mix nitroanthraquinone sulfonation pre-treatment, remove after most of by product, recycle a small amount of polar solvent refining, and adopt polar solvent secondary to apply mechanically technique, solve the problems referred to above, when reducing production costs, also improved quality product.
The technical solution that realizes the object of the invention is: a kind of 1-aminoanthraquinone process for refining, comprise the following steps: 1. from nitrated dilution, the mixing nitroanthraquinone that distillation ethylene dichloride finishes starts, in water medium, add sulphonating agent, in PH=8-9,95～100 ℃ of temperature are carried out sulfonation processing, then cool to 80 ℃ of following filtrations, water washing, oven dry; 2. the dry product after gained sulfonation is placed in polar solvent, is warmed up to 135-140 ℃ and once dissolves refiningly, then cools to the washing of 50 ℃ of filtrations, polar solvent; 3. the wet product after washing is again placed in polar solvent and carries out secondary and dissolve refiningly, and mother liquor and washing lotion are applied mechanically; 4. again through sodium sulfide reducing, filtration, water washing, dry to obtain 1-aminoanthraquinone product.
The sulphonating agent of above-mentioned steps described in is 1. S-WAT, and the mixing nitroanthraquinone after described giving money as a gift and the mass ratio of S-WAT are 1:(0.20～0.30).
The polar solvent of above-mentioned steps described in is 2. dimethyl formamide or N,N-DIMETHYLACETAMIDE, mixing nitroanthraquinone after described sulfonation and polar solvent total mass ratio are 1:(1.60～2.05), wherein, the mass ratio between the polar solvent that primary purification and secondary refining adopt is 1:(0.42～0.48).
Advantage of the present invention is:
Refining filtering mother liquor of the present invention is used for applying mechanically or distillating recovering solvent, refining after the total recovery of 1-aminoanthraquinone reach 74.5-75%, filter gained filtrate and washing lotion, can directly overlap for next batch produce or after treatment Distillation recovery recycle.The selected sulphonating agent of this technique, polar solvent have good selective removal ability to other useless organic impurity such as nitro by product, compare products obtained therefrom purity with former technique, yield obviously improves, and processing ease, produce very stablely, simultaneously production cost significantly reduces; Adopt after this technique, more than 1-aminoanthraquinone purity to 99.50%, yield improves more than 10%, reduced the generation of waste residue, meanwhile, a small amount of approximately 5% slag, purity is to 90-93%, can solve waste residue and process a difficult problem directly as the intermediate use of other kind dyestuff, produced again certain economic benefit simultaneously.The total production cost of 1-aminoanthraquinone can reduce more than 10%, is a production technique with considerable economic worth.
Embodiment
Below in conjunction with embodiment, the present invention is further described specifically, but is not limited to this.
1-aminoanthraquinone refining process of the present invention, its concrete steps are: from nitrated dilution, the mixing nitroanthraquinone that distillation ethylene dichloride finishes starts, in water medium, add sulphonating agent, in PH=8-9, 95～100 ℃ of temperature are carried out sulfonation processing, cool to again 80 ℃ of following filtrations, water washing, dry, dry product after gained sulfonation is in polar solvent, be warmed up to 135-140 ℃ of dissolving, cool to again 50 ℃ of filtrations, solvent wash, dividing secondary to carry out solvent applies mechanically refining, mother liquor and washing lotion are applied mechanically, again through sodium sulfide reducing, filter, water washing, dry to obtain 1-aminoanthraquinone product.
embodiment 1:
In the four-hole boiling flask of 1000ml, add mixing nitroanthraquinone after the nitrated 200g(ash content 2.5% of giving money as a gift), water 300ml,, be warmed up to 80-85 ℃, more slowly add S-WAT 60g, reinforced end, in PH=8-9, continue to be warmed up to 90-95 ℃, insulation reaction 2 hours, cool to below 80 ℃, filter, wash, dry, obtain the mixing nitroanthraquinone dry product 158g after sulfonation, yield 81%.
In the four-hole boiling flask of 250ml, add above-mentioned sulfonation to process rear dry product mixing nitroanthraquinone 119g, then add dimethyl formamide 135ml, be warmed up to 135-140 ℃, insulation reaction 1 hour, the 50 ℃ of filtrations of lowering the temperature, drain, then with the washing of 45ml dimethyl formamide, drain.
Above-mentioned wet product filter cake is transferred in the four-hole boiling flask of 250ml, and secondary adds dimethyl formamide 60ml, and secondary temperature elevation is to 135-140 ℃, insulation reaction 1 hour, the 50 ℃ of filtrations of lowering the temperature, drains, then with dimethyl formamide 20ml washing, drain, finally, with 90 ℃ of hot washes of 40ml, drain, obtain 1-nitroanthraquinone fine work filter cake, filter cake is through adding water making beating, and sodium sulfide reducing, filtration, washing, oven dry, obtain 1-aminoanthraquinone product 96.2g, purity 99.70%, yield 74.63%.
embodiment 2:
By the feeding intake and operating of embodiment 1, in the four-hole boiling flask of 1000ml, add mixing nitroanthraquinone after the nitrated 200g(ash content 2.5% of giving money as a gift), water 300ml, is warmed up to 80-85 ℃, then adds S-WAT 40g, reinforced end, in PH=8-9, continue to be warmed up to 90-95 ℃, insulation reaction 2 hours, cool to below 80 ℃, filter, wash, dry, obtain the mixing nitroanthraquinone dry product 160g after sulfonation, yield 82%.
In the four-hole boiling flask of 250ml, add above-mentioned sulfonation to process rear dry product mixing nitroanthraquinone 119g, then add dimethyl formamide 120ml, be warmed up to 135-140 ℃, insulation reaction 1 hour, lowers the temperature, filters, drains, with dimethyl formamide 21ml washing, drain again.
Rising wet product filter cake is transferred in the four-hole boiling flask of 250ml, and secondary adds dimethyl formamide 40ml, is again warmed up to 135-140 ℃, insulation reaction 1 hour, lower the temperature 50 ℃, filter, drain, with the washing of 20ml dimethyl formamide, drain, last, with 90 ℃ of hot washes of 40ml, drain, obtain 1-nitroanthraquinone fine work filter cake, filter cake adds water making beating again, through sodium sulfide reducing, filtration, washing, oven dry, obtain 1-aminoanthraquinone dry product 96.3g, purity 99.61%, yield 74.71%.
embodiment 3:
By the feeding intake and operating of embodiment 1, in the four-hole boiling flask of 1000ml, add mixing nitroanthraquinone after the nitrated 200g that gives money as a gift, sulfonation mother liquor 100ml(includes S-WAT 16g), primary wash liquor 200ml applies mechanically, and adds up to 300ml, is warmed up to 80-85 ℃, add S-WAT 35g, reinforced end, in PH=8-9 again, continue to be warmed up to 90-95 ℃, insulation reaction 2 hours, cools to below 80 ℃, filters, washs, dries, obtain the mixing nitroanthraquinone dry product 159g after sulfonation, yield 81.5%.
In the four-hole boiling flask of 250ml, dry product mixing nitroanthraquinone 119g after adding above-mentioned sulfonation to process, add again dimethyl formamide secondary refining filtrated stock, washing lotion (by 65% solvent, be that solvent is 59-62mL) apply mechanically and novel solvent dimethyl formamide, add up to folding 120ml, be warmed up to 135-140 ℃, insulation reaction 1 hour, lower the temperature, filter, drain, then wash, drain with dimethyl formamide 45ml.
Rising wet product filter cake is transferred in the four-hole boiling flask of 250ml, and secondary adds dimethyl formamide 60ml, and secondary temperature elevation is to 135-140 ℃, insulation reaction 1 hour, lower the temperature 50 ℃, filter, drain, then wash with dimethyl formamide 20ml, drain, last, with 90 ℃ of hot washes of 40ml, drain, obtain 1-nitroanthraquinone fine work filter cake, then add water making beating, through sodium sulfide reducing, filtration, washing,, dry to obtain 1-aminoanthraquinone finished product 96.7g, content 99.58%, yield 75.02%.
embodiment 4:
Feeding intake and operating by embodiment 2, in the four-hole boiling flask of 1000ml, add mixing nitroanthraquinone after the nitrated 200g(ash content 2.5% of giving money as a gift), sulfonation mother liquor 100ml(includes S-WAT 16g), primary wash liquor 200ml applies mechanically, add up to 300ml, be warmed up to 80-85 ℃, add S-WAT 40g, reinforced end, in PH=8-9 again, continue to be warmed up to 90-95 ℃, insulation reaction 2 hours, cools to below 80 ℃, filters, washs, dries, obtain the mixing nitroanthraquinone dry product 159g after sulfonation, yield 81.5%.
In the four-hole boiling flask of 250ml, dry product mixing nitroanthraquinone 119g after adding sulfonation to process, add again N,N-DIMETHYLACETAMIDE secondary fine mother liquor, washing lotion (by 65% solvent) to apply mechanically and novel solvent N,N-DIMETHYLACETAMIDE, add up to folding 135ml, be warmed up to 135-140 ℃, insulation reaction 1 hour, lowers the temperature, filters, drains, then washs, drains with 45ml N,N-DIMETHYLACETAMIDE.
Above-mentioned wet product filter cake adds N,N-DIMETHYLACETAMIDE 60ml again, and secondary temperature elevation is to 135-140 ℃, insulation reaction 1 hour, lower the temperature 50 ℃, filter, drain, with the washing of 20ml N,N-DIMETHYLACETAMIDE, last again, with 90 ℃ of hot washes of 40ml, drain, 1-nitroanthraquinone fine work filter cake, add water making beating, then through sodium sulfide reducing, filtration, washing, dry to obtain 1-aminoanthraquinone finished product 96.5g, content 99.57%, yield 74.86%.
Claims (3)
1. a 1-aminoanthraquinone process for refining, it is characterized in that comprising the following steps: 1. from nitrated dilution, the mixing nitroanthraquinone that distillation ethylene dichloride finishes starts, in water medium, add sulphonating agent, in PH=8-9,95～100 ℃ of temperature are carried out sulfonation processing, then cool to 80 ℃ of following filtrations, water washing, oven dry; 2. the dry product after gained sulfonation is placed in polar solvent, is warmed up to 135-140 ℃ and once dissolves refiningly, then cools to the washing of 50 ℃ of filtrations, polar solvent; 3. the wet product after washing is again placed in polar solvent and carries out secondary and dissolve refiningly, and mother liquor and washing lotion are applied mechanically; 4. again through sodium sulfide reducing, filtration, water washing, dry to obtain 1-aminoanthraquinone product.
2. 1-aminoanthraquinone process for refining according to claim 1, is characterized in that the sulphonating agent described in step is 1. S-WAT, and the mixing nitroanthraquinone after described giving money as a gift and the mass ratio of S-WAT are 1:(0.20～0.30).
3. 1-aminoanthraquinone process for refining according to claim 1, it is characterized in that the polar solvent described in step is 2. dimethyl formamide or N,N-DIMETHYLACETAMIDE, mixing nitroanthraquinone after described sulfonation and polar solvent total mass ratio are 1:(1.60～2.05), wherein, the mass ratio between the polar solvent that primary purification and secondary refining adopt is 1:(0.42～0.48).
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| CN201310634840.9A CN103694126A (en) | 2013-12-02 | 2013-12-02 | Process for refining 1-amino-anthraquinone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086430A (en) * | 2014-07-18 | 2014-10-08 | 中国人民解放军防化学院 | Method for synthesizing 1-aminoanthraquinone |
| CN110668930A (en) * | 2019-10-24 | 2020-01-10 | 江苏亚邦染料股份有限公司 | Production method of benanthrone |
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| US2302729A (en) * | 1941-04-05 | 1942-11-24 | Du Pont | Process of purifying 1-nitroanthraquinone |
| JPS5344550A (en) * | 1976-09-28 | 1978-04-21 | Sumitomo Chem Co Ltd | Preparation of aminoanthraquinone |
| CN101838204A (en) * | 2010-04-28 | 2010-09-22 | 盐城市瓯华化学工业有限公司 | Novel process for controlling waste residue and recycling resources in 1-anthraquinone production |
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2013
- 2013-12-02 CN CN201310634840.9A patent/CN103694126A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2302729A (en) * | 1941-04-05 | 1942-11-24 | Du Pont | Process of purifying 1-nitroanthraquinone |
| JPS5344550A (en) * | 1976-09-28 | 1978-04-21 | Sumitomo Chem Co Ltd | Preparation of aminoanthraquinone |
| CN101838204A (en) * | 2010-04-28 | 2010-09-22 | 盐城市瓯华化学工业有限公司 | Novel process for controlling waste residue and recycling resources in 1-anthraquinone production |
Non-Patent Citations (3)
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| 吉林染料厂: "非均相法硝化还原制1-氨基蒽醌的试验研究", 《染料与染色》 * |
| 张劲松: "溶剂法生产1-硝基蒽醌及其衍生物的工业化――纪念溶剂法1-硝基蒽醌工艺研制成功二十年", 《染料与染色》 * |
| 王子鹏: "溶剂法生产1-氨基蒽醌新工艺", 《化工时刊》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086430A (en) * | 2014-07-18 | 2014-10-08 | 中国人民解放军防化学院 | Method for synthesizing 1-aminoanthraquinone |
| CN104086430B (en) * | 2014-07-18 | 2016-08-24 | 中国人民解放军防化学院 | A kind of synthetic method of 1-amino anthraquinones |
| CN110668930A (en) * | 2019-10-24 | 2020-01-10 | 江苏亚邦染料股份有限公司 | Production method of benanthrone |
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Application publication date: 20140402 |