CN85100335B - Method to manufacture 1, 4-naphthoquinone by liquid phase oxidation of naphthaline - Google Patents
Method to manufacture 1, 4-naphthoquinone by liquid phase oxidation of naphthaline Download PDFInfo
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- CN85100335B CN85100335B CN85100335A CN85100335A CN85100335B CN 85100335 B CN85100335 B CN 85100335B CN 85100335 A CN85100335 A CN 85100335A CN 85100335 A CN85100335 A CN 85100335A CN 85100335 B CN85100335 B CN 85100335B
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Abstract
The present invention relates to a method for preparing 1, 4-naphthoquinone by the liquid-phase oxidation of naphthaline, which belongs to the preparation method of organic compounds. The present invention adopts an indirect electric oxidation method for the process of preparing the 1, 4-naphthoquinone from naphthaline, ceric sulfate-sulphuric acid is used as oxidant, aliphatic hydrocarbon of which the boiling range is from 80 to 140 DEG C is used as a solvent, and the naphthaline is oxidized to form the 1, 4-naphthoquinone in an intermittent or continuous mode under the conversion rate from 25 to 70% of the naphthaline; after reaction is completed, a product of 1, 4-naphthoquinone is precipitated by cooling from an organic phase, and a water phase containing cerous cerium of sulfur acid is electrolyzed and regenerated after extraction; an organic solvent is recovered and reused. The present invention is suitable for producing the naphthaquinone by an intermittent or continuous method in industry.
Description
The invention belongs to the preparation method of organic compound.
1,4-naphthoquinones (hereinafter to be referred as naphthoquinones) is an organic intermediate, and its preparation can be adopted the vapour phase oxidation process of naphthalene or reclaim from the tail gas of Tetra hydro Phthalic anhydride production.Vapour phase oxidation process can generate the naphthoquinones and the Tetra hydro Phthalic anhydride of equivalent to the poor selectivity of naphthoquinones in the reaction.Naphthoquinones content in the tail gas is very low.Reclaim difficulty.
Adopt liquid phase oxidation, the reaction conditions gentleness, good to the selectivity of naphthoquinones, the high valence ion that especially adopts variable valence is after oxygenant is oxidized to naphthoquinones with naphthalene, ion has bigger superiority through electrolytic process oxidation regeneration (being the indirect electrooxidation method) at a low price, has avoided three-waste pollution.
Technological process in the past generates 4.6～5.4% 1-nitro-naphthalene by product (ICI, English Patent 1192037,1203434) when adopting ceric ammonium nitrate-salpeter solution to be oxygenant oxidation naphthalene.When being oxygenant oxidation naphthalene, also can generate 8～10% nitro-naphthalene by product (Dimond Shamrook Corp, European patent 75828) with cerous nitrate-salpeter solution.When adopting ceric nitrate-salpeter solution to be oxygenant, the volume of material is big, space time yield is 1.6～2.9g/Lhr(ICI only, English Patent 1192037) product aftertreatment complexity, the method that will pass through alkali cleaning, drying or steam distillation or vacuum distilling obtains product (ICI English Patent 1192037,1203434,1360904).Even carry out oxidizing reaction without organic solvent, after reaction finished, still needing went out product with organic solvent extraction, obtains solid naphthoquinones (British Columbia Research Council, Canadian Patent 1132996) through aforesaid method again.Oxidising process is intermittence or many stills serial operation (ICI, English Patent 1192037), the scale operation difficulty.
The object of the present invention is to provide an intermittence or continuous mode, be fit to the method for suitability for industrialized production naphthoquinones.
It is oxygenant that the present invention adopts ceric sulfate-sulphuric acid soln (hereinafter to be referred as water).Raw naphthalene material is dissolved in the water-insoluble inert organic solvents (hereinafter to be referred as organic phase), under fully stirring, carries out oxidizing reaction.Reaction finishes, water after water-insoluble inert organic solvents extraction, in electrolyzer with inferior cerium ion (Ce(III)) electrolytic regeneration is high cerium ion (Ce(IV)), be reused for the naphthalene oxidising process, the solid naphthoquinones is separated out in the organic phase cooling, and solvent recuperation is used again.
Used organic solvent should be the water-insoluble inert organic solvents.This solvent and water do not dissolve each other and have strong oxidation-resistance, to naphthalene certain solubleness should be arranged in addition, and the solubleness to naphthoquinones are bigger when hot, and the solubleness to naphthoquinones when cold is less again.The used water-insoluble inert organic solvents of the present invention is the aliphatic hydrocarbon of 80～140 ℃ of boiling ranges, and its characteristics are that reacted naphthoquinones can directly cool off and separate out.
For fast reaction speed and the peroxidation that prevents naphthoquinones take place, should keep the high density of naphthalene.Adopt the method for low naphthalene per pass conversion, can reach the ideal effect, the per pass conversion of naphthalene is 20～70%, preferably 25～40%.
The feed ratio of ceric sulfate and naphthalene directly influences the transformation efficiency of reaction times and naphthalene.It is 2: 1～6: 1 preferably 3: 1～4: 1 that the present invention adopts the mol proportioning of ceric sulfate and naphthalene.
Oxidising process has the reaction of high order district continuously, carries out in the tower that has impeller to stir.
Be added with fixedly column plate in the tower, tower is divided into 13～16 order reaction districts, the height in every order reaction district is 0.9～1.1 times of tower diameter.Will guarantee reactant biphase thorough mixing and mobile relatively in reaction zone, water is added by cat head, and the reaction back is gone out by tower bottom flow; Organic phase adds at the bottom of by tower, and the reaction back is flowed out by cat head.At the bottom of the cat head of oxidizing tower and tower phase separation region is arranged respectively, it highly is 1～4.5 times of tower diameter.
The length of oxidation time has certain influence to the space time yield and the quality of naphthoquinones.In continuous oxidation, the material mean residence time is 3～9 minutes.In intermittent oxidation, decide on different feed ratio, be generally 4～60 minutes.
The a small amount of naphthoquinones of aqueous phase dissolved after the naphthalene oxidation is 80～140 ℃ of aliphatic hydrocarbon extractions with boiling range.Guaranteeing the high yield of naphthoquinones, and avoid that naphthoquinones is decomposed in electro-oxidation process on anode, consumed power.The extraction usefulness quantity of solvent be water heavy 1/16～1/23.
Extraction process carries out in extraction tower.By adding at the bottom of the tower, the water after the naphthalene oxidation is added by cat head after the organic solvent preheating.Behind the counter-current extraction, organic solvent is flowed out by cat head, and after the solid naphthoquinones was separated out in cooling, solvent recuperation was used again.Water is gone out by tower bottom flow, enters the electrolyzer oxidation regeneration.
Oxidation and extraction are all carried out under 60～80 ℃.
The solid naphthoquinones that cooling is separated out is at first used 5～10 times of washings to naphthoquinones weight, uses 1～5 times of above-mentioned organic solvent drip washing to naphthoquinones weight again, filters drying.Naphthoquinones purity is greater than 95%, and yield 75～83%(is in the naphthalene of conversion) space time yield 6～42g/Lhr.
The water that contains inferior cerium ion after the naphthalene oxidation is high cerium ion through electrolytic regeneration, is reused for oxidising process.Electrolytic regeneration carries out in the electrolyzer that porous porcelain tube or cation exchange membrane are arranged.Electrolyzer middle-jiao yang, function of the spleen and stomach very ceramic matrix is electroplated lead peroxide, and negative electrode is lead or 2RK65 acid-resistant stainless steel.Use the 2RK65 acid-resistant stainless steel to have the low advantage of groove pressure drop.In order to guarantee the good mass-transfer of electrolytic solution, except that other method of employing, can adopt the method for air or nitrogen bubble at anode surface.Current efficiency is 85～96%.
Example 1
Get ceric sulfate 12.6g(0.0312mol) be dissolved in the 125ml 1M sulphuric acid soln.Organic phase is naphthalene 2g(0.0156mol) be dissolved in the aliphatic solvents of 80～140 ℃ of 20ml boiling ranges.Water is joined in the there-necked flask that has stirring and thermometer, start stirring, be warming up to 70 ℃.Add organic phase, reacted 7 minutes.Water phase separated and organic phase.Make the organic phase cooling separate out the solid naphthoquinones.The water organic solvent extraction.Naphthoquinones yield 23.9%(is by the naphthalene that adds), space time yield 35g/Lhr.
Example 2
Get the 1M sulphuric acid soln 94ml(ceNo.0312mol of ceric sulfate), organic phase is naphthalene 1g(0.0078mol) be dissolved in the aliphatic solvents of 80～140 ℃ of 20ml boiling ranges, all the other are with example 1.Naphthoquinones yield 59.0%(is by the naphthalene that adds), purity 95%.
Example 3
Be reflected in the above-mentioned oxidizing tower and carry out, tower body amasss 650ml.Material is preheating to 65～70 ℃ before advancing tower, and the tower chuck is incubated to 68～70 ℃.Organic phase is that the boiling range that contains naphthalene 83% is 80～140 ℃ a aliphatic hydrocarbon; Water is the 1M sulphuric acid soln of the high cerium 5.9% of sulfur acid.Water is added by cat head with the flow of 157ml/Min, and organic phase adds at the bottom of by tower with the flow of 18.4ml/Min, stirs reaction down.Reacted water is gone out by tower bottom flow, enters extraction tower, and organic phase is flowed out by cat head, and the solid naphthoquinones is separated out in cooling, and organic solvent reclaims and uses.
Extraction is carried out in extraction tower.The above-mentioned organic solvent that does not contain naphthalene adds at the bottom of by tower, and the water after the naphthalene oxidation is added by cat head.Extraction tower and oxidizing tower keep same temperature.Behind the counter-current extraction, water is gone out by tower bottom flow, enters the electrolyzer oxidation regeneration; After the solid naphthoquinones is separated out in the organic phase cooling, reclaim and use again.
The solid naphthoquinones, washs with 2 times of above-mentioned organic solvents that do not contain naphthalene to naphthoquinones weight after the filtration at twice with 6 times of washings to naphthoquinones weight, filters.Reclaim solvent, drying.Naphthoquinones purity 95.3%, yield 82.4%(is by the naphthalene that transforms), space time yield 41.8g/Lhr, naphthalene single-pass conversion 39%.
Example 4
Inferior cerium ion electrolytic regeneration carries out in the cation exchange membrane electrolyzer.Electroplating lead peroxide with ceramic matrix is anode, is negative electrode with lead, and electrolytic solution is the 1M sulphuric acid soln of the inferior cerium 0.2M of sulfur acid.The heavy 348g of positive column electrolytic solution, the heavy 117g of cathodic area electrolytic solution.Start impeller and stir, keep 57～59 ℃ of temperature, electrolysis 54 minutes.Inferior cerium ion has 75.3% to be converted into high cerium ion, and current efficiency is 95.8%.
Example 5
Electrolyzer is the plastic barrel of diameter 75mm, and interior is barrier film with the porous porcelain tube, and negative electrode is the 2RK65 acid-resistant stainless steel, and all the other conditions are with example 4, groove pressure drop 3.0～3.2V, and current efficiency is 93%.
Example 6
Electrolyzer is the plastic barrel of diameter 75mm, adopts the air bubbling to stir, and the air consumption is 0.4m
3/ hr, all the other conditions are with example 4, and current efficiency is 92%.
Claims (7)
1, the present invention system prepares the process of naphthoquinones about naphthalene through indirect electrooxidation, is the oxidant reaction preparation with ceric sulfate-sulfuric acid, it is characterized in that with aliphatic hydrocarbon be solvent, behind continuous oxidation reaction, cools off organic phase, separates out the product naphthoquinones.
2, process according to claim 1 is characterized in that aliphatic solvents is the aliphatic hydrocarbon of 80～140 ℃ of boiling ranges.
3, process according to claim 1, the per pass conversion that it is characterized in that naphthalene is 20～40%.
4, process according to claim 1 is characterized in that the continuous oxidation reaction time is 3～9 minutes.
5, process according to claim 1, its continuous oxidation reaction tie up in the oxidizing tower carries out.
6, equipment according to claim 5 is characterized in that oxidizing tower has 13～16 order reaction districts, and every order reaction district height is 0.9～1.1 times of tower diameter.
7, equipment according to claim 5 is characterized in that at the bottom of the cat head of oxidizing tower and the tower phase separation region being arranged respectively, and its phase separation region height is 1.0～4.5 times of tower diameter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100335A CN85100335B (en) | 1985-04-01 | 1985-04-01 | Method to manufacture 1, 4-naphthoquinone by liquid phase oxidation of naphthaline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN85100335A CN85100335B (en) | 1985-04-01 | 1985-04-01 | Method to manufacture 1, 4-naphthoquinone by liquid phase oxidation of naphthaline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85100335A CN85100335A (en) | 1986-08-13 |
| CN85100335B true CN85100335B (en) | 1988-03-09 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN85100335A Expired CN85100335B (en) | 1985-04-01 | 1985-04-01 | Method to manufacture 1, 4-naphthoquinone by liquid phase oxidation of naphthaline |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955217B (en) * | 2010-05-31 | 2012-05-09 | 北京颖新泰康国际贸易有限公司 | Preparation method of menadione nicotinamide bisulfite |
| CN104887677B (en) * | 2014-03-05 | 2018-10-26 | 复旦大学 | Natural naphthoquinones dimer and its purposes in preparing antibacterials |
| CN109400456A (en) * | 2018-10-30 | 2019-03-01 | 四川锐华科技有限公司 | A kind of preparation method of Isosorbide-5-Nitrae naphthoquinones |
| CN109265333B (en) * | 2018-11-20 | 2021-09-07 | 四川省银河化学股份有限公司 | Preparation method of beta-menadione |
| CN109438209B (en) * | 2018-11-27 | 2022-02-22 | 青岛泰玛新材料科技有限公司 | Method and equipment for continuously synthesizing quinone compounds in tubular reactor |
| CN109521148A (en) * | 2019-01-25 | 2019-03-26 | 四川双启检测技术有限公司 | A kind of method of 1,4- naphthoquinones content in detection menadione |
| CN111892490A (en) * | 2020-06-18 | 2020-11-06 | 兄弟科技股份有限公司 | Ce4+Method for preparing beta-menadione and its derivative menadione sodium bisulfite as oxidant |
| CN112626547B (en) * | 2020-12-25 | 2021-10-15 | 浙江工业大学 | Method for indirect electrosynthesis of quinone compounds by utilizing ultrasound assistance |
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1985
- 1985-04-01 CN CN85100335A patent/CN85100335B/en not_active Expired
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| Publication number | Publication date |
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| CN85100335A (en) | 1986-08-13 |
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