CN104086372A - Technology for preparing hydroquinone through diazotation hydrolysis method - Google Patents
Technology for preparing hydroquinone through diazotation hydrolysis method Download PDFInfo
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- CN104086372A CN104086372A CN201410268301.2A CN201410268301A CN104086372A CN 104086372 A CN104086372 A CN 104086372A CN 201410268301 A CN201410268301 A CN 201410268301A CN 104086372 A CN104086372 A CN 104086372A
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- resorcinol
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- sulfuric acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/12—Diazo compounds, i.e. compounds having the free valencies of >N2 groups attached to the same carbon atom
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A technology for preparing hydroquinone through a diazotation hydrolysis method relates to the technical field of the chemical industry. The technology comprises the following steps: reacting a diazo liquid obtained after a reaction of sulfuric acid, p-aminophenol, sodium nitrite, urea and thiourea with sulfuric acid with the concentration of 30%, extracting, and processing to obtain hydroquinone. The technology has the advantages of convenient and simple preparation, environmental protection, no pollution, easily available materials, less equipment investment, high purity and convenient operation, and the prepared hydroquinone has the advantages of good use effect, safety and reliability.
Description
Technical field
The present invention relates to chemical technology field, be specifically related to the technique that diazonium hydrolysis method is prepared Resorcinol.
Background technology
Resorcinol, organic compound, white crystals, meets naked light, high hot flammable.Combustion decomposition is carbon monoxide, carbonic acid gas.Can react with strong oxidizer, be subject to the pyrolytic decomposition poisonous gas of emitting, it is of many uses: 1. Resorcinol is mainly as the photographic developer of taking a picture.Resorcinol and alkylide thereof are widely used in the stopper that monomer transporting procedures adds, and conventional concentration is about 200ppm.Monomethyl ether of hydroquinone is the intermediate of edible oil antioxidant BHA; Hydroquinone dimethyl ether is the intermediate of dyestuff, pigment dyestuff and spices; Resorcinol diethyl ether is the intermediate of photopigment, dyestuff.Resorcinol is also for producing N, and N-diphenyl-para-phenylene diamine is for the oxidation inhibitor of rubber and gasoline and anti-smelly dose.2. be used as the oxidation inhibitor of rubber and gasoline, dyestuff intermediate etc.3. process field, is added on quinhydrones in the hot water and water coolant of closed circuit heating and cooling system, to water side metal, can play corrosion inhibition.The oxygen scavenger of stove water for quinhydrones adds quinhydrones wherein, to remove remaining dissolved oxygen when feedwater preheating deoxygenation.4. the stopper of the resin such as vinylbenzene, divinyl, isoprene, vinyl acetate between to for plastic, vinyl cyanide or rubber monomer, conventional concentration is about 200 * 10-6 also as producing black-and-white development agent, anthraquinone dye, azoic dyestuff, rubber antioxidant, stablizer and oxidation inhibitor etc.5. as vinylbenzene, esters of acrylic acid, graft neoprene adhesives, vinyl cyanide and the stopper of other vinyl monomers and terminator or the stablizer of high temperature emulsion polymerization.Also as phenolic aldehyde? the oxidation inhibitor of butyronitrile sizing agent, gasoline dispersion stabilizer, the photographic developer of cinefilm, photograph, X ray sheet, rubber antioxidant, the oxidation inhibitor of grease and phenolic aldehyde, butyronitrile sizing agent, the stablizer of coating and varnish etc.Also be the raw material of manufacturing anthraquinone dye, azoic dyestuff, medicine and hair dye.6. as the photographic developer in photoengraving, for electroplating interpolation.7. as inhibiter, stablizer and the oxidation inhibitor etc. of washing composition, also for the hair dye of makeup.8. produce black-and-white development agent, anthraquinone dye, azoic dyestuff, rubber antioxidant, stablizer and oxidation inhibitor.9. photometry phosphorus, magnesium, niobium, copper, silicon and arsenic etc.The polarography of iridium and volumetric determination.The reductive agent of heteropolyacid, copper and golden reductive agent.Traditional Process of Hydroquinone Production technique is comparatively complicated, and environmental pollution is larger, and the purity of producing is lower, is difficult to meet human wants.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of purity high, and the simple diazonium hydrolysis method of preparation technology is prepared the technique of Resorcinol.
Technical problem to be solved by this invention realizes by the following technical solutions:
Diazonium hydrolysis method is prepared a technique for Resorcinol, it is characterized in that: comprise following processing step,
(1) diazotization reaction
A. the p-aminophenol of the sulfuric acid of 15% concentration and 98% dropped in reactor and stir, then cooling the temperature to-5-0 ℃.
B. temperature in the kettle being dripped to concentration is 40% sodium nitrite in aqueous solution, time for adding 30～45min.
C. dropwise rear insulation 30min, and will wherein add urea again to stir 15min.
D. in still, nitrogen is emitted when not obvious, to adding thiocarbamide to continue to stir 15min in still, obtains Vandyke brown diazo liquid, stand-by in 0 ℃ of preservation.
(2) hydrolysis reaction
A. the sulfuric acid of 30% concentration is added in reactor and temperature in the kettle is risen to 106～108 ℃ and then reflux.
B. the diazo liquid of (one) system is dropped in reactor, the time is controlled at 60min, at 102～104 ℃ of insulation 3～8h that reflux.
C. the solution in above-mentioned b is down to the light brown hydrolyzed solution that normal temperature obtains Resorcinol.
(3) extracting and separating
Choose methyl iso-butyl ketone (MIBK) and be divided into 6 parts, according to the ratio of 3:1:1:1, be divided into the hydrolyzed solution 4 times above-mentioned (two) being made and extract, obtain red-brown extraction oil reservoir and raffinate water layer and then water layer is removed.
(4) aftertreatment
A. the NaHCO3 solution of 1% concentration is washed until pH value is 5 the oil reservoir producing in above-mentioned (three).
B. reactor is vacuumized and pressure is adjusted to 0.085MPa and carry out precipitation 30min, then pressure is adjusted to 0.095MPa and continues precipitation 60min.
C. the temperature of reactor is risen to 250 ℃ rapidly, the thick Resorcinol distilling in still is collected.
D. by adding gac, zinc powder in the thick Resorcinol in step c, be warming up to 80～85 ℃, then add 30% sulfuric acid, continue backflow 30-60min.
E. the solution in steps d is filtered, filtering gac wherein, then filtrate naturally cools in 25 ℃ of input crystallization kettles and carries out crystallization, obtains Resorcinol finished product packing warehouse-in after being then dried.
The sulfuric acid containing in aqueous layer extracted in described step (three) carries out normal pressure dehydration and is concentrated into 30% concentration, recycles.
The invention has the beneficial effects as follows: the present invention is easy to prepare simple, and environment friendly and pollution-free, raw material is easy to get, and facility investment is few, and purity is high, convenient operation, the Ortho Anisidine result of use of preparation is good, safe and reliable.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below in conjunction with specific embodiment, further set forth the present invention.
Diazonium hydrolysis method is prepared a technique for Resorcinol, comprises following processing step,
(1) diazotization reaction
A. the p-aminophenol of the sulfuric acid of 15% concentration and 98% dropped in reactor and stir, then cooling the temperature to-5-0 ℃.
B. temperature in the kettle being dripped to concentration is 40% sodium nitrite in aqueous solution, time for adding 30～45min.
C. dropwise rear insulation 30min, and will wherein add urea again to stir 15min.
D. in still, nitrogen is emitted when not obvious, to adding thiocarbamide to continue to stir 15min in still, obtains Vandyke brown diazo liquid, stand-by in 0 ℃ of preservation.
(2) hydrolysis reaction
A. the sulfuric acid of 30% concentration is added in reactor and temperature in the kettle is risen to 106～108 ℃ and then reflux.
B. the diazo liquid of (one) system is dropped in reactor, the time is controlled at 60min, at 102～104 ℃ of insulation 3～8h that reflux.
C. the solution in above-mentioned b is down to the light brown hydrolyzed solution that normal temperature obtains Resorcinol.
(3) extracting and separating
Choose methyl iso-butyl ketone (MIBK) and be divided into 6 parts, according to the ratio of 3:1:1:1, be divided into the hydrolyzed solution 4 times above-mentioned (two) being made and extract, obtain red-brown extraction oil reservoir and raffinate water layer and then water layer is removed.The sulfuric acid containing in aqueous layer extracted carries out normal pressure dehydration and is concentrated into 30% concentration, recycles.
(4) aftertreatment
A. the NaHCO3 solution of 1% concentration is washed until pH value is 5 the oil reservoir producing in above-mentioned (three).
B. reactor is vacuumized and pressure is adjusted to 0.085MPa and carry out precipitation 30min, then pressure is adjusted to 0.095MPa and continues precipitation 60min.
C. the temperature of reactor is risen to 250 ℃ rapidly, the thick Resorcinol distilling in still is collected.
D. by adding gac, zinc powder in the thick Resorcinol in step c, be warming up to 80～85 ℃, then add 30% sulfuric acid, continue backflow 30-60min.
E. the solution in steps d is filtered, filtering gac wherein, then filtrate naturally cools in 25 ℃ of input crystallization kettles and carries out crystallization, obtains Resorcinol finished product packing warehouse-in after being then dried.
More than show and described ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification sheets, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (2)
1. diazonium hydrolysis method is prepared a technique for Resorcinol, it is characterized in that: comprise following processing step,
(1) diazotization reaction
A. the p-aminophenol of the sulfuric acid of 15% concentration and 98% dropped in reactor and stir, then cooling the temperature to-5-0 ℃.
B. temperature in the kettle being dripped to concentration is 40% sodium nitrite in aqueous solution, time for adding 30～45min.
C. dropwise rear insulation 30min, and will wherein add urea again to stir 15min.
D. in still, nitrogen is emitted when not obvious, to adding thiocarbamide to continue to stir 15min in still, obtains Vandyke brown diazo liquid, stand-by in 0 ℃ of preservation.
(2) hydrolysis reaction
A. the sulfuric acid of 30% concentration is added in reactor and temperature in the kettle is risen to 106～108 ℃ and then reflux.
B. the diazo liquid of (one) system is dropped in reactor, the time is controlled at 60min, at 102～104 ℃ of insulation 3～8h that reflux.
C. the solution in above-mentioned b is down to the light brown hydrolyzed solution that normal temperature obtains Resorcinol.
(3) extracting and separating
Choose methyl iso-butyl ketone (MIBK) and be divided into 6 parts, according to the ratio of 3:1:1:1, be divided into the hydrolyzed solution 4 times above-mentioned (two) being made and extract, obtain red-brown extraction oil reservoir and raffinate water layer and then water layer is removed.
(4) aftertreatment
A. the NaHCO3 solution of 1% concentration is washed until pH value is 5 the oil reservoir producing in above-mentioned (three).
B. reactor is vacuumized and pressure is adjusted to 0.085MPa and carry out precipitation 30min, then pressure is adjusted to 0.095MPa and continues precipitation 60min.
C. the temperature of reactor is risen to 250 ℃ rapidly, the thick Resorcinol distilling in still is collected.
D. by adding gac, zinc powder in the thick Resorcinol in step c, be warming up to 80～85 ℃, then add 30% sulfuric acid, continue backflow 30-60min.
E. the solution in steps d is filtered, filtering gac wherein, then filtrate naturally cools in 25 ℃ of input crystallization kettles and carries out crystallization, obtains Resorcinol finished product packing warehouse-in after being then dried.
2. a kind of diazonium hydrolysis method according to claim 1 is prepared the technique of Resorcinol, it is characterized in that: the sulfuric acid containing in aqueous layer extracted in described step (three) carries out normal pressure dehydration and is concentrated into 30% concentration, recycles.
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| CN201410268301.2A CN104086372A (en) | 2014-06-16 | 2014-06-16 | Technology for preparing hydroquinone through diazotation hydrolysis method |
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| CN201410268301.2A CN104086372A (en) | 2014-06-16 | 2014-06-16 | Technology for preparing hydroquinone through diazotation hydrolysis method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341275A (en) * | 2014-10-24 | 2015-02-11 | 盐城市鼎烨化工有限公司 | Synthesis method for 2, 6-dihydroxytoluene |
-
2014
- 2014-06-16 CN CN201410268301.2A patent/CN104086372A/en active Pending
Non-Patent Citations (1)
| Title |
|---|
| 沈发治: "对氨基苯酚重氮化水解法制备对苯二酚", 《广东化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341275A (en) * | 2014-10-24 | 2015-02-11 | 盐城市鼎烨化工有限公司 | Synthesis method for 2, 6-dihydroxytoluene |
| CN104341275B (en) * | 2014-10-24 | 2016-05-18 | 江苏鼎烨药业有限公司 | A kind of synthetic method of 2,6-orcin |
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Application publication date: 20141008 |