CN85100335A - Naphthalene liquid-phase oxidation system 1, the method for 4-naphthoquinones - Google Patents
Naphthalene liquid-phase oxidation system 1, the method for 4-naphthoquinones Download PDFInfo
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- CN85100335A CN85100335A CN 85100335 CN85100335A CN85100335A CN 85100335 A CN85100335 A CN 85100335A CN 85100335 CN85100335 CN 85100335 CN 85100335 A CN85100335 A CN 85100335A CN 85100335 A CN85100335 A CN 85100335A
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Abstract
Naphthalene liquid-phase oxidation system 1, the 4-naphthoquinones belongs to the preparation method of organic compound.
The present invention adopts the indirect electrooxidation method by naphthalene system 1, the process of 4-naphthoquinones.Employing ceric sulfate-sulfuric acid is oxygenant, and the aliphatic hydrocarbon that boiling range is 80～140 ℃ is a solvent, naphthalene transformation efficiency 25～70% times, with intermittently or continuous mode naphthalene is oxidized to 1, the 4-naphthoquinones, after reaction finished, organic phase was separated out product 1 through cooling, the 4-naphthoquinones; Water electrolytic regeneration after extracting of the inferior cerium of sulfur acid; Organic solvent reclaims and uses.
The present invention is applicable to industrial intermittence or continuous processing production naphthoquinones.
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 one 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 one salpeter solution.When adopting ceric sulfate one sulphuric acid soln 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 one 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.Organic solvent gives the heat back by adding at the bottom of the tower, and the water after the naphthalene oxidation is added by cat head.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 125mLM sulphuric acid soln.Organic phase is naphthalene 2g(0.0156Mol) be dissolved in the aliphatic solvents of 80～140 ℃ of 20mL boiling ranges.Water joined to have stir and during three mouthfuls of thermometer burn also, 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(Ce IV 0.0312Mol 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 gives heat 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; 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 (13)
1, the present invention system prepares the process of naphthoquinones about naphthalene through indirect electrooxidation, it is characterized in that with ceric sulfate one sulphuric acid soln be oxygenant, and aliphatic hydrocarbon is a solvent, with reacting at intermittence or successive mode.After the cooling organic phase was separated out naphthoquinones, solvent used repeatedly, and water is through extraction, and electrolytic regeneration is reused for oxidising process.
2, process according to claim 1 is characterized in that solvent 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 20～70%.
4, process according to claim 1 is characterized in that the mole ratio that feeds intake of ceric sulfate and naphthalene is 2: 1～6: 1.
5, process according to claim 1 is characterized in that continuous oxidising process carries out in the oxidizing tower that the reaction of high order district is arranged.
6, process 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, process 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 it highly is 1～4.5 times of tower diameter.
8, process according to claim 1 is characterized in that water after the naphthalene oxidation in extraction tower, and with the aliphatic hydrocarbon extraction of 80～140 ℃ of boiling ranges, the aliphatic hydrocarbon consumption is 1/23～1/16 of a water weight.
9, process according to claim 1 is characterized in that the reaction times is 3～9 minutes in the continuous mode of oxidizing; The reaction times is 4～60 minutes in the intermittent oxidation mode.
10, process according to claim 1 is characterized in that the electrolytic regeneration cation exchange membrane electrolyzer of inferior cerium ion.
11, process according to claim 1 is characterized in that inferior cerium ion electrolytic regeneration does negative electrode with the 2RK65 acid-resistant stainless steel.
12, process according to claim 1 is characterized in that inferior cerium ion electrolytic regeneration stirs with air or nitrogen bubble mode, and its consumption is 9-10dm
3/ hrCm
2The electrolyzer cross section.
13, continuous mode of oxidizing proposed by the invention is characterized in that the ceric water of sulfur acid is added by the oxidizing tower cat head, and the organic phase that contains naphthalene adds at the bottom of by the oxidation Tata.After the reaction, the water that contains inferior cerium ion is gone out by tower bottom flow, enters extraction tower by cat head, and the water-insoluble inert organic solvents adds at the bottom of extracting Tata.Behind the counter-current extraction, water goes out to enter electrolytic tank electrolysis regeneration by tower bottom flow, and the organic phase after the extraction is flowed out by the extraction tower cat head, and after naphthoquinones was separated out in cooling, solvent recuperation was used again.Organic phase after the naphthalene oxidation is flowed out by the oxidizing tower cat head, and after naphthoquinones was separated out in cooling, solvent recuperation was used again.
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 |
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| CN85100335A true CN85100335A (en) | 1986-08-13 |
| CN85100335B CN85100335B (en) | 1988-03-09 |
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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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955217A (en) * | 2010-05-31 | 2011-01-26 | 北京颖新泰康国际贸易有限公司 | Preparation method of menadione nicotinamide bisulfite |
| CN104887677A (en) * | 2014-03-05 | 2015-09-09 | 复旦大学 | Natural naphthoquinone dimer and uses of natural naphthoquinone dimer in preparation of antibacterial drugs |
| CN109265333A (en) * | 2018-11-20 | 2019-01-25 | 四川省银河化学股份有限公司 | A kind of preparation method of β-menadione |
| 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 |
| CN109438209A (en) * | 2018-11-27 | 2019-03-08 | 青岛泰玛新材料科技有限公司 | A kind of method and apparatus continuously synthesizing quinones 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 |
| CN112626547A (en) * | 2020-12-25 | 2021-04-09 | 浙江工业大学 | Method for indirect electrosynthesis of quinone compounds by utilizing ultrasound assistance |
-
1985
- 1985-04-01 CN CN85100335A patent/CN85100335B/en not_active Expired
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101955217A (en) * | 2010-05-31 | 2011-01-26 | 北京颖新泰康国际贸易有限公司 | Preparation method of menadione nicotinamide bisulfite |
| 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 |
| CN104887677A (en) * | 2014-03-05 | 2015-09-09 | 复旦大学 | Natural naphthoquinone dimer and uses of natural naphthoquinone dimer in preparation of antibacterial drugs |
| 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 |
| CN109265333A (en) * | 2018-11-20 | 2019-01-25 | 四川省银河化学股份有限公司 | A kind of preparation method of β-menadione |
| 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 |
| CN109438209A (en) * | 2018-11-27 | 2019-03-08 | 青岛泰玛新材料科技有限公司 | A kind of method and apparatus continuously synthesizing quinones in tubular reactor |
| 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 |
| CN112626547A (en) * | 2020-12-25 | 2021-04-09 | 浙江工业大学 | Method for indirect electrosynthesis of quinone compounds by utilizing ultrasound assistance |
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| Publication number | Publication date |
|---|---|
| CN85100335B (en) | 1988-03-09 |
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