CN1962593A - Pyrocatechin and hydroquinone production process - Google Patents
Pyrocatechin and hydroquinone production process Download PDFInfo
- Publication number
- CN1962593A CN1962593A CN 200610070195 CN200610070195A CN1962593A CN 1962593 A CN1962593 A CN 1962593A CN 200610070195 CN200610070195 CN 200610070195 CN 200610070195 A CN200610070195 A CN 200610070195A CN 1962593 A CN1962593 A CN 1962593A
- Authority
- CN
- China
- Prior art keywords
- aminophenol
- resorcinol
- pyrocatechol
- ortho
- extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention discloses a cleaning preparing technique to manufacture catechol and hydroquinone, which comprises the following steps: adopting o (p-)-nitrochlorobenzene as raw material; pressurizing the sodium hydroxide to obtain o (p-)-nitrophenol through hydrolyzing; hydrogenating under nickel catalyst; producing the product under acid catalyst in the water dielectric; avoiding high-salt and nitro waste water effectively as well as high-density hydrogen dioxide solution.
Description
Technical field
The invention belongs to field of fine chemical, relate to the production technique of fine-chemical intermediate, relate in particular to a kind of pyrocatechol and Process of Hydroquinone Production technology of cleanliness without any pollution.
Background technology
Pyrocatechol is the important intermediate of producing new high-efficiency carbamate chemicals for agriculture carbofuran (furans pellet), Propoxur, the mould prestige of second, it also is the important source material of producing spices piperonylaldehyde, vanillin food grade,1000.000000ine mesh, in addition, at field pyrocatechols such as oxidation inhibitor, sensitive materials, medicine, dyestuffs demand is arranged also.
Resorcinol is mainly used in synthetic sensitive materials, anthraquinone, fertilizer additive, synthetic materials stopper, oxidation inhibitor and rubber ingredients etc.
At present, pyrocatechol and Process of Hydroquinone Production technology mainly contain following several:
1. ortho chloro phenol hydrolysis system pyrocatechol:
2. aniline oxidation, reduction:
3. phenol hydrogen peroxide oxidation:
The ortho chloro phenol hydrolysis produces a large amount of waste water, heavy contamination, yield is low, and the aniline oxidation produces a large amount of waste water, waste residue, and cost is also very high, the phenol-hydrogen peroxide oxidation, the hydrogen peroxide of employing 50-70% is the security of guaranteeing to produce, on equipment, require very high, invest bigger, and, because of per pass conversion lower, phenol, pyrocatechol, Resorcinol mask work are very huge, must bring energy consumption bigger.
Summary of the invention
The purpose of this invention is to provide a kind of cleaning pyrocatechol little, that cost is low and production technique of Resorcinol polluted.
The invention provides a kind of pyrocatechol or Process of Hydroquinone Production technology, comprising: the hydrolysis in aqueous sodium hydroxide solution of ortho-nitrochlorobenzene or para-nitrochloro-benzene prepares o-NP or p-NP, o-NP or p-NP prepare Ortho-Aminophenol or p-aminophenol, Ortho-Aminophenol or p-aminophenol direct hydrolysis production pyrocatechol or Resorcinol under an acidic catalyst effect through shortening.
The invention provides the production technique of a kind of pyrocatechol and Resorcinol, comprise the following steps:
(1) ortho-nitrochlorobenzene or para-nitrochloro-benzene through pressurized hydrolysis, are used hcl acidifying then in aqueous sodium hydroxide solution, and the accent pH value is 1-2;
(2) o-NP that obtains of step (1) or p-NP be under the nickel catalyzator effect, hydrogenation, preparation Ortho-Aminophenol or p-aminophenol;
(3) step (2) obtains Ortho-Aminophenol or p-aminophenol in water medium, under an acidic catalyst effect, temperature 210-250 ℃ of reaction 3-10 hour;
(4) product of step (3) is transferred pH value 1-2, filters, and filtrate is used solvent extraction, and extraction liquid reclaims extraction agent by distillation, and bottoms is pyrocatechol or Resorcinol crude product; In the reaction solution after the extraction, Ortho-Aminophenol or p-aminophenol content are 0～0.1% (weight ratio);
(5) rectifying under 1-30mmHg vacuum tightness of pyrocatechol or Resorcinol obtains pure pyrocatechol or Resorcinol.
Technological line of the present invention can be represented with following equation:
Preferably, the concentration of the aqueous sodium hydroxide solution described in the step (1), para-nitrochloro-benzene lioh hydrolysis na concn is 137-140g/L, ortho-nitrochlorobenzene lioh hydrolysis na concn is 79-81g/L.
Preferably, the pressure of the pressurized hydrolysis described in the step (1), the pressure of preparation o-NP is 0.5-0.7MPa, the pressure of preparation p-NP is 0.65-0.9MPa.
Preferably, the concentration of the hydrochloric acid described in the step (1) is 30% technical hydrochloric acid.
Adjacent (to) the nitro Benzene Chloride is by after the traditional technology hydrolysis, produce a large amount of contain the neighbour (to) waste water of nitrophenols, about the about 200g/L of interior sodium chloride-containing, discharge serious environment pollution, the present invention after extraction, oxidation, complexing, decolouring series of process are handled, obtains high purity chlorination sodium water solution with the waste water of o-NP in the step (1) or the generation of p-NP production process, can be used for sodium chloride electrolysis and produce chlor-alkali, also can reclaim sodium-chlor and use as Industrial Salt.
Preferably, extraction agent is many alkyl tertiary amines solvent oil system or many alkyl tertiary amines alkylaromatic hydrocarbon system, n-Octanol solvent oil system or n-Octanol alkylaromatic hydrocarbon system.
Described many alkyl tertiary amines solvent oil system is the double solvents of many alkyl tertiary amines and solvent oil; Described many alkyl tertiary amines alkylaromatic hydrocarbon system is the double solvents of many alkyl tertiary amines and alkylaromatic hydrocarbon; Described n-Octanol solvent oil system is the double solvents of n-Octanol and solvent oil; Described n-Octanol alkylaromatic hydrocarbon system is the double solvents of n-Octanol and alkylaromatic hydrocarbon; Described solvent oil is available from Jinan Refinery.
Preferably, oxygenant is a potassium permanganate, and its consumption is that thousand of waste water weight/0. 1 are to thousandth.
Preferably, described many alkyl tertiary amines are N
235Or trioctylamine.
Preferably, in the step 1), the waste water that produces in o-NP or the p-NP production process is through descending octanol: after 200# solvent oil (3: the 7) extraction, use potassium permanganate oxidation at 50-80 ℃ again, use the Fe in the NaOH precipitation system then
3+, Mn
2+, after activated carbon decolorizing obtains the water white transparency sodium chloride solution, nitro thing content drops to below the 0.5PPm, and this salt solution can return sodium chloride electrolysis system preparing chlorine gas and sodium hydroxide, and also recyclable sodium-chlor is as Industrial Salt.Described 200# solvent oil is available from Jinan Refinery.
Preferably, the weight ratio of the described o-NP of step (2) or p-NP and nickel catalyzator is 30: 1.
Preferably, an acidic catalyst described in the step (3) is a kind of in sulfuric acid, phosphoric acid, hydrochloric acid, sodium bisulfite, the monoammonium sulfate.
Preferably, the molar ratio of the described Ortho-Aminophenol of step (3) or p-aminophenol and an acidic catalyst is Ortho-Aminophenol or p-aminophenol: an acidic catalyst=1: 0.5-1.5; Described Ortho-Aminophenol or p-aminophenol shared weight ratio in reaction system is 5-20%, and water shared weight ratio in reaction system is 70-90%.。
Preferably, Ortho-Aminophenol described in the step (3) or p-aminophenol, an acidic catalyst, water add in the reactor in described ratio, are heated to 210-250 ℃, are incubated 3-10 hour, the generation neighbour (to) dihydroxy-benzene, reaction cools to below 50 ℃ after finishing, and transfers pH=1-2, filter, filtrate extracts with extraction agent, and extraction liquid reclaims extraction agent by distillation, bottoms also be the neighbour (to) the dihydroxy-benzene crude product.
Preferably, adjacent (to) dihydroxy-benzene rectifying under 1-30mmHg vacuum tightness obtain pure neighbour (to) dihydroxy-benzene.
Described extraction agent is a kind of in butylacetate, butanols, the n-butyl ether
Described reaction solution through extract the neighbour (to) dihydroxy-benzene, again through extraction reclaim not have reaction the neighbour (to) amino-phenol, reclaim ammonium salt behind the activated carbon decolorizing, the water that steams returns in the feed proportioning system prepares burden.
Described neighbour (to) amino-phenol during hydrolysis, can adopt the indirect type mode of production under catalyst action, also can adopt the continous way mode of production, continous way can adopt automatization control.As long as be satisfied with temperature of reaction, reaction times.
With pipeline that material contacts, reactor, interchanger material therefor in the described reaction system is a kind of or its matrix material in tantalum, zirconium, the tetrafluoroethylene.
The present invention compared with prior art has following advantage: solved adjacent (to) high saliferous in the nitrophenols production process, contain the pollution problem of nitro thing waste water, avoided aniline oxidation, the high pollution problem of original production Resorcinol also, also avoided phenol with the high density hydrogen peroxide oxidation produce adjacent (to) safety problem of dihydroxy-benzene.Substantially do not have processing wastewater in the production process and efflux, pollution-free; Processing condition are easy to control, are easy to industrial automation and scale operation; The product yield height, quality is good; The present invention than phenol hydrogen peroxide oxidation system neighbour (to) about the low 10-20% of dihydroxy-benzene production cost.
Embodiment
Following examples are to further specify of the present invention, but the present invention is not limited thereto.
Embodiment 1:
The preparation of o-NP: add 150 parts in folding hundred sodium hydroxide in the autoclave, the aqueous sodium hydroxide solution of concentration 80g/L adds 250 parts of ortho-nitrochlorobenzenes again, be heated to 140-150 ℃, the about 0.45MPa of pressure, be incubated 2 hours, be warmed up to material 155-160 ℃ again, pressure is about 0.54, is incubated 3 hours.Cooling to about 120 ℃, material is pressed onto in the reactor that liner acid-proof ceramic tile and band titanium spiral coil cooling tube and titanium stir, is 1-2 with the 30% hydrochloric acid PH that neutralizes, and cools to 30 ℃, and suction filtration obtains 210 parts of the damp product of o-NP, and content is about 92%, yield 90-95%.The umber of described raw material is weight part.
Ortho-Aminophenol preparation: 300 parts of o-NPs, 1000 part of 95% ethanol, 9 parts of activatory nickel catalyzators, closed reactor, be heated to about 80 ℃, under the 1-1.5MPa hydrogen-pressure, temperature control is no more than 100 ℃, after treating to inhale hydrogen hardly, add 1 part of activatory nickel catalyzator, logical hydrogen cools to 80 ℃ till do not inhale hydrogen, through titanium accurate filter elimination catalyzer, crystallisation by cooling, centrifugal, oven dry obtain Ortho-Aminophenol.Filtrate also can obtain some Ortho-Aminophenols through reclaiming ethanol, and yield is at 90-95% after twice merging.The umber of described raw material is weight part.
The pyrocatechol preparation: 100 parts of Ortho-Aminophenols, 120 part of 30% hydrochloric acid, 780 parts of water are in lining zirconium reactor, be heated to 230 ℃, 230-250 ℃ of temperature control 6 hours, cool to 50 ℃, filter, filtrate is used n-butyl acetate extraction, reclaim butylacetate, resistates underpressure distillation under 25mmHg obtains 86 parts of pure pyrocatechols, content 99.3%, yield 85-90%.The umber of described raw material is weight part.
Embodiment 2:
With embodiment 1, difference is:
The preparation of pyrocatechol: 100 parts of Ortho-Aminophenols, 92 part of 98% sulfuric acid, 808 parts of water are put into the zirconium reactor, be heated to 235 ℃, 235-240 ℃ of temperature control 3 hours, cool to 50 ℃, filter, filtrate is used n-butyl acetate extraction, reclaim butylacetate, resistates underpressure distillation under 25mmHg gets 88 parts of pure pyrocatechols, content 99.7%, yield 85-90%.The umber of described raw material is weight part.
Embodiment 3:
With embodiment 1, difference is:
The preparation of pyrocatechol: 108 parts of Ortho-Aminophenols, 230 parts of monoammonium sulfates, 1700 parts of water are put into the zirconium reactor, be heated to 240 ℃, 240-242 ℃ of temperature control 4 hours, cool to 40-50 ℃, filter, filtrate extracts with n-butyl ether, reclaim n-butyl ether, resistates underpressure distillation under 25mmHg obtains pure pyrocatechol, content 99.8/5, yield 99.1%.The umber of described raw material is weight part.
Embodiment 4:
With embodiment 1, difference is:
The preparation of pyrocatechol: 108 parts of Ortho-Aminophenols, 60 parts of sodium bisulfites, 1700 parts of water are put into the zirconium reactor, be heated to 240 ℃, 240-242 ℃ of temperature control 4 hours, cool to 40-50 ℃, filter, filtrate extracts with butanols, reclaim propyl carbinol, resistates underpressure distillation under 25mmHg obtains pure pyrocatechol, content 99.8/5, yield 80-88%.The umber of described raw material is weight part.
Embodiment 5:
The preparation of p-NP: add in the autoclave and contain 325 parts in sodium hydroxide, the aqueous sodium hydroxide solution of concentration 137-140g/L, add 600 parts of para-nitrochloro-benzenes again, be heated to 155-160 ℃, the about 0.55MPa of pressure, the hydrolysis reaction heat release, pressure rises to 0.8MPa (if pressure rises again, answer row pressure), be incubated 3 hours, row pressure is pressed into reaction solution in the reactor of liner acid-proof ceramic tile to pressure 0.2MPa again, be 1-2 with the 30% hydrochloric acid PH that neutralizes then, cool to about 30 ℃, suction filtration obtains about 500 parts of p-NP tide product, content is about 92%, yield 90-95%.The umber of described raw material is weight part.
P-aminophenol preparation: 250 parts of p-NPs, 1000 part of 95% ethanol, 7 parts of activatory nickel catalyzators, closed reactor, be heated to about 80-90 ℃, logical hydrogen under the 1-1.5MPa hydrogen-pressure, temperature control is no more than 100 ℃, after treating to inhale hydrogen hardly, add 1 part of activatory nickel catalyzator, logical again hydrogen cools to 80 ℃ till do not inhale hydrogen, through titanium accurate filter elimination catalyzer, crystallisation by cooling, centrifugal, oven dry obtain p-aminophenol.Filtrate also can obtain some p-aminophenol through reclaiming ethanol, obtains 180 parts of p-aminophenol after twice merging, yield 90-95%.The umber of described raw material is weight part.
The Resorcinol preparation: 100 parts of p-aminophenol, 120 part of 30% hydrochloric acid, 780 parts of water are in lining zirconium reactor, be heated to 230 ℃, after 5 hours, lower the temperature at 230-250 ℃ of temperature control, filter, filtrate is used n-butyl acetate extraction, behind the recovery butylacetate, obtain the Resorcinol crude product, under 20mmHg vacuum tightness, underpressure distillation obtains 88 parts of pure Resorcinol, content 99.48%, yield 80-90%.The umber of described raw material is weight part.
Embodiment 6:
With embodiment 5, difference is:
The preparation of Resorcinol: 100 parts of p-aminophenol, 92 part of 98% sulfuric acid, 808 parts of water are in the reactor of lining zirconium, be heated to 230 ℃, 230-235 ℃ of temperature control 2.5 hours, drop to 50 ℃, filter, filtrate is used ethyl acetate extraction, reclaim ethyl acetate, resistates underpressure distillation under 25mmHg gets 90 parts of pure Resorcinol, content 99.8%, yield 85-90%.The umber of described raw material is weight part.
Embodiment 7:
With embodiment 5, difference is:
The preparation of Resorcinol: 108 parts of p-aminophenol, 190 parts of Sodium Pyrosulfites, 1600 parts of water are in the reactor of lining zirconium, be heated to 220 ℃, 220-230 ℃ of temperature control 6 hours, drop to 40-50 ℃, filter, filtrate is used n-butanol extraction, reclaim propyl carbinol, resistates underpressure distillation under 25mmHg obtains 79 parts of pure Resorcinol, content 99.9%, yield 75-80%.The umber of described raw material is weight part.
Embodiment 8:
With embodiment 5, difference is:
The preparation of Resorcinol: 108 parts of p-aminophenol, 60 parts of sodium bisulfites, 1600 parts of water are in the reactor of lining zirconium, be heated to 220 ℃, 220-230 ℃ of temperature control 6 hours, drop to 40-50 ℃, filter, filtrate is used n-butanol extraction, reclaim propyl carbinol, resistates underpressure distillation under 25mmHg obtains 79 parts of pure Resorcinol, content 99.9%, yield 75-84%.The umber of described raw material is weight part.
Embodiment 9:
Adjacent (to) the nitrobenzene waste water processing: adjacent (to) nitrophenol wastewater and extraction agent (n-Octanol: 200# solvent oil=3: 7), in 5: 1 ratios (weight ratio) through three grades of extractions of centrifugal extractor adverse current, waste water after the extraction adds 0.5 ‰ potassium permanganate, at 50-80 ℃ of oxidation 0.5-2 hour, stirred 0.5 hour by the gac that adds 1 ‰, transfer the about 7-8 of PH with NaOH, through the pressure filter press filtration, the filtrate water white transparency, nitrophenol content is less than 0.5PPm in the filtrate, and this sodium chloride aqueous solution was mixed into electrolyzer with normal salt solution by 1: 2, through running in 1 month, chlorine, liquid caustic soda does not detect unusual phenomenon, electrolyzer, the also no abnormal phenomenon of electrode.
Embodiment 10:
Adjacent (to) the nitrobenzene waste water processing: adjacent (to) nitrophenol wastewater and extraction agent (n-Octanol: 200# solvent oil=3: 7), in 5: 1 ratios (weight ratio) through three grades of extractions of centrifugal extractor adverse current, waste water after the extraction adds 0.2 ‰ potassium permanganate, at 50-80 ℃ of oxidation 0.5-2 hour, stirred 0.5 hour by the gac that adds 1 ‰, transfer the about 7-8 of PH with NaOH, through the pressure filter press filtration, the filtrate water white transparency, nitrophenol content is less than 0.5PPm in the filtrate, and this sodium chloride aqueous solution was mixed into electrolyzer with normal salt solution by 1: 2, through running in 1 month, chlorine, liquid caustic soda does not detect unusual phenomenon, electrolyzer, the also no abnormal phenomenon of electrode.
Embodiment 11:
Adjacent (to) the nitrobenzene waste water processing: adjacent (to) nitrophenol wastewater and extraction agent, in 5: 1 ratios (weight ratio) through three grades of extractions of centrifugal extractor adverse current, waste water after the extraction adds 0.9 ‰ potassium permanganate, at 50-80 ℃ of oxidation 0.5-2 hour, stirred 0.5 hour by the gac that adds 1 ‰, transfer the about 7-8 of PH with NaOH, through the pressure filter press filtration, the filtrate water white transparency, nitrophenol content is less than 0.5PPm in the filtrate, and this sodium chloride aqueous solution was mixed into electrolyzer with normal salt solution by 1: 2, through running in 1 month, chlorine, liquid caustic soda does not detect unusual phenomenon, electrolyzer, the also no abnormal phenomenon of electrode.
Embodiment 12:
The recovery of ammonia chloride: hydrolyzed solution condensing crystal after extracting obtains ammonium chloride, and the water that steams returns feed proportioning system and applies mechanically.
Claims (10)
1. pyrocatechol or Process of Hydroquinone Production technology comprise: the hydrolysis in aqueous sodium hydroxide solution of ortho-nitrochlorobenzene or para-nitrochloro-benzene prepares o-NP or p-NP, o-NP or p-NP and prepares Ortho-Aminophenol or p-aminophenol, Ortho-Aminophenol or p-aminophenol direct hydrolysis under an acidic catalyst effect is produced pyrocatechol or Resorcinol through shortening.
2. the production technique of pyrocatechol as claimed in claim 1 or Resorcinol comprises the following steps:
(1) ortho-nitrochlorobenzene or para-nitrochloro-benzene through pressurized hydrolysis, are used hcl acidifying then in aqueous sodium hydroxide solution, and the accent pH value is 1-2;
(2) o-NP that obtains of step (1) or p-NP be under the nickel catalyzator effect, hydrogenation, preparation Ortho-Aminophenol or p-aminophenol;
(3) step (2) obtains Ortho-Aminophenol or p-aminophenol in water medium, under an acidic catalyst effect, temperature 210-250 ℃ of reaction 3-10 hour;
(4) product of step (3) is transferred pH value 1-2, filters, and filtrate extracts with extraction agent, and extraction liquid reclaims extraction agent by distillation, and the bottoms after the distillation is pyrocatechol or Resorcinol crude product; In the reaction solution after the extraction, the weight content of pyrocatechol or Resorcinol is 0～0.1%;
(5) bottoms pyrocatechol or the rectifying under 1-30mmHg vacuum tightness of Resorcinol crude product obtain pure pyrocatechol or Resorcinol in the step (4).
3. require the production technique of 1 or 2 described pyrocatechols or Resorcinol as letter of authorization, it is characterized in that: the waste water that o-NP or p-NP production process produce in the step (1), after extraction, oxidation, complexing, decolouring series of process are handled, obtain high purity chlorination sodium water solution, can be used for sodium chloride electrolysis and produce chlor-alkali, also can reclaim sodium-chlor and use as Industrial Salt.
4. require the production technique of 3 described pyrocatechols or Resorcinol as letter of authorization, it is characterized in that: the extraction agent that described extraction is used is many alkyl tertiary amines solvent oil system or many alkyl tertiary amines alkylaromatic hydrocarbon system, n-Octanol solvent oil system or n-Octanol alkylaromatic hydrocarbon system; The oxygenant that described oxidation is used is potassium permanganate, and its consumption is that thousand of waste water weight/0. 1 are to thousandth.
5. require the production technique of 4 described pyrocatechols or Resorcinol as letter of authorization, it is characterized in that: described many alkyl tertiary amines are N
235Or trioctylamine.
6. the production technique of pyrocatechol as claimed in claim 2 or Resorcinol is characterized in that: an acidic catalyst described in the step (3) is a kind of in sulfuric acid, phosphoric acid, hydrochloric acid, sodium bisulfite, the monoammonium sulfate.
7. the production technique of pyrocatechol as claimed in claim 2 or Resorcinol is characterized in that: the molar ratio of Ortho-Aminophenol or p-aminophenol and an acidic catalyst is in the step (3): Ortho-Aminophenol or p-aminophenol: an acidic catalyst=1: 0.5-1.5;
Described Ortho-Aminophenol or p-aminophenol shared weight ratio in whole reaction system is 5-20%, and water shared weight ratio in whole reaction system is 70-90%.
8. as the production technique of claim 7 or 8 described pyrocatechols or Resorcinol, it is characterized in that: described Ortho-Aminophenol or p-aminophenol, an acidic catalyst, water add in the reactor in proportion, be heated to 210-250 ℃, be incubated 3-10 hour down at 210-250 ℃, produce pyrocatechol or Resorcinol, reaction cools to 50 ℃ after finishing, it is 1-2 that reaction solution is transferred PH, filter, filtrate extracts with extraction agent, extraction liquid is by distillating recovering solvent, and bottoms is pyrocatechol or Resorcinol crude product.
9. the production technique of pyrocatechol as claimed in claim 9 or Resorcinol is characterized in that: described extraction agent is a kind of in butylacetate, butanols, the n-butyl ether; Waste water behind extraction pyrocatechol or the Resorcinol reclaims ammonium salt behind condensing crystal, the water Returning reacting system that steams is applied mechanically.
10. the production technique of pyrocatechol as claimed in claim 1 or 2 or Resorcinol is characterized in that: with material institute contact arrangement material in the described reaction system be a kind of or its matrix material in tantalum, zirconium, the tetrafluoroethylene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100701952A CN100391922C (en) | 2006-11-24 | 2006-11-24 | Pyrocatechin and hydroquinone production process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100701952A CN100391922C (en) | 2006-11-24 | 2006-11-24 | Pyrocatechin and hydroquinone production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1962593A true CN1962593A (en) | 2007-05-16 |
| CN100391922C CN100391922C (en) | 2008-06-04 |
Family
ID=38081843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100701952A Expired - Fee Related CN100391922C (en) | 2006-11-24 | 2006-11-24 | Pyrocatechin and hydroquinone production process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100391922C (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412662B (en) * | 2007-10-16 | 2011-06-01 | 江苏扬农化工集团有限公司 | Method for preparing p-dihydroxy benzene |
| CN102344372A (en) * | 2011-07-29 | 2012-02-08 | 江苏力达宁化工有限公司 | Synthetic method of o-nitrophenol and o-nitroanisole |
| CN102838457A (en) * | 2012-09-20 | 2012-12-26 | 山东潍坊润丰化工有限公司 | Synthesis method of 2, 5-dichlorophenol |
| CN102910757A (en) * | 2012-09-27 | 2013-02-06 | 新泰昊原化工有限责任公司 | Treatment technique of waste water generated in production of o-nitrophenol |
| CN103215613A (en) * | 2013-04-07 | 2013-07-24 | 重庆大学 | Method for producing hydroquinone through electrocatalytic reduction of p-benzoquinone |
| CN103304380A (en) * | 2013-04-27 | 2013-09-18 | 中国中化股份有限公司 | Production process for continuously hydrolyzing and producing hydroquinone through multi-kettles in series |
| CN103466873A (en) * | 2013-09-30 | 2013-12-25 | 河南龙成煤高效技术应用有限公司 | Method for processing sewage with high-concentration phenol and ammonia |
| CN103804205A (en) * | 2013-12-23 | 2014-05-21 | 济南塑邦精细化工有限公司 | Novel technology for preparing ortho-aminophenol |
| CN103880602A (en) * | 2012-12-19 | 2014-06-25 | 中国中化股份有限公司 | Technology for producing hydroquinone by hydrolysis of p-aminophenol through continuous method |
| CN108218727A (en) * | 2017-12-29 | 2018-06-29 | 烟台安诺其精细化工有限公司 | The preparation method of o-aminophenol |
| CN111138420A (en) * | 2020-02-10 | 2020-05-12 | 北京凯吉特医药科技发展有限公司 | C13Isotope labeled lapatinib synthesis method |
| CN113321227A (en) * | 2021-08-02 | 2021-08-31 | 清大国华环境集团股份有限公司 | Recycling method of bromine-containing aromatic hydrocarbon hazardous waste |
| CN116023237A (en) * | 2022-12-08 | 2023-04-28 | 复旦大学 | Continuous preparation method of hydroquinone in water phase |
-
2006
- 2006-11-24 CN CNB2006100701952A patent/CN100391922C/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101412662B (en) * | 2007-10-16 | 2011-06-01 | 江苏扬农化工集团有限公司 | Method for preparing p-dihydroxy benzene |
| CN102344372A (en) * | 2011-07-29 | 2012-02-08 | 江苏力达宁化工有限公司 | Synthetic method of o-nitrophenol and o-nitroanisole |
| CN102838457A (en) * | 2012-09-20 | 2012-12-26 | 山东潍坊润丰化工有限公司 | Synthesis method of 2, 5-dichlorophenol |
| CN102910757A (en) * | 2012-09-27 | 2013-02-06 | 新泰昊原化工有限责任公司 | Treatment technique of waste water generated in production of o-nitrophenol |
| CN103880602A (en) * | 2012-12-19 | 2014-06-25 | 中国中化股份有限公司 | Technology for producing hydroquinone by hydrolysis of p-aminophenol through continuous method |
| CN103215613A (en) * | 2013-04-07 | 2013-07-24 | 重庆大学 | Method for producing hydroquinone through electrocatalytic reduction of p-benzoquinone |
| CN103304380A (en) * | 2013-04-27 | 2013-09-18 | 中国中化股份有限公司 | Production process for continuously hydrolyzing and producing hydroquinone through multi-kettles in series |
| CN103304380B (en) * | 2013-04-27 | 2015-08-26 | 中国中化股份有限公司 | Multi-floating bodies continuous hydrolysis produces the production technique of Resorcinol |
| CN103466873A (en) * | 2013-09-30 | 2013-12-25 | 河南龙成煤高效技术应用有限公司 | Method for processing sewage with high-concentration phenol and ammonia |
| CN103466873B (en) * | 2013-09-30 | 2015-09-02 | 河南龙成煤高效技术应用有限公司 | A kind of process is containing the method for high-concentration phenol, ammonia sewage |
| CN103804205A (en) * | 2013-12-23 | 2014-05-21 | 济南塑邦精细化工有限公司 | Novel technology for preparing ortho-aminophenol |
| CN103804205B (en) * | 2013-12-23 | 2016-08-24 | 济南塑邦精细化工有限公司 | A kind of technique preparing o-aminophenol |
| CN108218727A (en) * | 2017-12-29 | 2018-06-29 | 烟台安诺其精细化工有限公司 | The preparation method of o-aminophenol |
| CN111138420A (en) * | 2020-02-10 | 2020-05-12 | 北京凯吉特医药科技发展有限公司 | C13Isotope labeled lapatinib synthesis method |
| CN113321227A (en) * | 2021-08-02 | 2021-08-31 | 清大国华环境集团股份有限公司 | Recycling method of bromine-containing aromatic hydrocarbon hazardous waste |
| CN116023237A (en) * | 2022-12-08 | 2023-04-28 | 复旦大学 | Continuous preparation method of hydroquinone in water phase |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100391922C (en) | 2008-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100391922C (en) | Pyrocatechin and hydroquinone production process | |
| CN108911960A (en) | A kind of preparation method of photoinitiator 1- hydroxycyclohexyl phenyl ketone | |
| CN110105220B (en) | Method for preparing m-phenylenediamine from meta-oil | |
| CN104592042A (en) | Clean technology for continuously synthesizing 2,4-binitro-6-chloroaniline | |
| CN103131862B (en) | Pretreatment decomposition method extracts high purity rare earth oxides from fluorescent powder scrap | |
| CN113429295A (en) | Method for preparing m-phenylenediamine by continuous catalytic hydrogenation based on fixed bed microreactor | |
| CN101607919B (en) | Method for producing anisidine by mixed nitrochlorobenzene reacting in aqueous solvent | |
| CN102993026B (en) | Preparation method of p-phenylenediamine | |
| CN101182390B (en) | Method for preparing disperse red 60 | |
| CN102826961A (en) | Cycling treatment method for waste acid produced in production of hydroquinone | |
| CN107162029B (en) | Red mud method of comprehensive utilization | |
| CN110668956B (en) | Method for desalting and purifying water phase through water washing extraction in RT base production process | |
| CN1861525B (en) | Treatment process of active hargil waste acid | |
| CN109748800A (en) | A kind of preparation method of pair of nitrobenzyl alcohol | |
| CN101798269A (en) | Preparation method for synthesizing 2,4-dichloroaniline from 2,4-dichloronitrobenzene | |
| CN105646261A (en) | Tetracaine preparation method | |
| CN105732687A (en) | Methyltris(methylethylketoxime)silane preparation method | |
| CN110204418A (en) | A kind of method of highly effective hydrogenation dechlorination purification trichloro-benzenes | |
| CN108752217A (en) | A kind of new synthetic method of Du Lutewei key intermediates 2,4- difluorobenzylamines | |
| CN101607917B (en) | Production method of high-quality p-aminophenol | |
| CN109265356B (en) | Method for producing o-phenylenediamine | |
| CN112479824A (en) | Method for recovering crystallization mother liquor in production process of 4-chloro-3, 5-dimethylphenol | |
| CN107556204A (en) | A kind of synthetic method of ambroxol hydrochloride | |
| CN106995382A (en) | A kind of method of catalytic hydrogenation production 3- methyl-PABA | |
| CN110606801A (en) | Method for continuously preparing vanillin and syringaldehyde |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Haoyuan Xintai Chemical Co., Ltd. Assignor: Wang Zaijun Contract record no.: 2011370000242 Denomination of invention: Pyrocatechin and hydroquinone production process Granted publication date: 20080604 License type: Exclusive License Open date: 20070516 Record date: 20110607 |
|
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Haoyuan Xintai Chemical Co., Ltd. Assignor: Wang Zaijun Contract record no.: 2011370000242 Date of cancellation: 20120709 |
|
| CP02 | Change in the address of a patent holder |
Address after: 266000, Shandong, Qingdao Pingdu New River eco chemical technology industry base, Feng Shui Road, No. 5 Patentee after: Wang Zaijun Address before: 250404 Pingyin Guang Li chemical plant, Diao Shan Po Town, Pingyin County, Ji'nan City, Shandong Province Patentee before: Wang Zaijun |
|
| CP02 | Change in the address of a patent holder | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080604 Termination date: 20181124 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |