CN102503777B - Post-treatment method of hydroquinone prepared by diazotization and hydrolysis of paraaminophenol - Google Patents
Post-treatment method of hydroquinone prepared by diazotization and hydrolysis of paraaminophenol Download PDFInfo
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Abstract
The invention provides a post-treatment method of hydroquinone prepared by diazotization and hydrolysis of paraaminophenol. The post-treatment method comprises the following steps of: (1) combining extraction oil phase extracted and separated from a reaction part with extraction oil from a step (6), desolventizing under the protection of nitrogen to a certain concentration, slowly cooling to a preset temperature, and crystallizing hydroquinone in a solvent; (2) separating crystal mixed liquid to obtain a crude product and a crystallization mother liquor; (3) decolorizing the hydroquinone crude product, carrying out heat separation, recrystallizing, separating, and drying to obtain hydroquinone; (4) carrying out back extraction to transfer hydroquinone in the crystallization mother liquor to a water layer obtained after back extraction; (5) desolventizing an oil layer obtained after back extraction to recover the solvent, and discharging kettle residues at the same time; and (6) combining the water layer obtained after back extraction with the recrystallizing mother liquor and extracting with the recovered solvent. The method provided by the invention has the advantages of simple flow, low investment, no need for negative-pressure high-temperature process, less tar, low energy consumption, high yield, low requirement on raw material purity, no wastewater generation and easiness in industrialization; the quality of the obtained product meets the national standard; and in particular, the solvent and water are well recycled, zero discharge is realized, and the production cost and environmental protection pressure are reduced.
Description
Technical field
The present invention relates to a kind of refining method of Resorcinol, more specifically, relate to a kind of method from p-aminophenol diazotization hydrolysis reaction product high-purity Resorcinol.
Background technology
Resorcinol claims again quinhydrones (HQ), it is a kind of conventional industrial chemicals, important source material, intermediate and the auxiliary agent of medicine, agricultural chemicals, dyestuff and rubber etc., be mainly used in producing photographic developer, anthraquinone dye, azoic dyestuff, rubber antioxidant and monomer stopper, food stabiliser and coating antioxidant, anticoagulant, synthetic ammonia catalyst etc., Application Areas is very extensive.
Resorcinol industrialized preparing process mainly contains aniline oxidation style, to diisopropyl benzene oxidation style, phenol-acetone method and hydoxylating phenol etc.The Resorcinol product that aniline oxidation style reaction generates need to make finished product through separated purification step such as concentrated, decolouring, extraction, crystallization, dry or rectifying, produces a large amount of waste residues, waste liquid, waste gas in production, and separation costs is high, and facility investment is high.P-Diisopropylbenzene oxidation style exists that raw material sources are limited, oxidising process has the shortcomings such as certain security risk, technical difficulty and investment intensity are large.Hydoxylating phenol exists that reaction yield is low, by product is many, coproduction pyrocatechol when producing Resorcinol, and production capacity is received the problems such as impact of the pyrocatechol market requirement.
In order to overcome above-mentioned shortcoming, we once p-aminophenol diazotization hydrolysis method prepare Resorcinol novel process and conduct in-depth research, and applied for Patents CN101412662B, its disclosed reactive moieties comprises following 3 concrete steps, (A) diazotization reaction: adopt to dripping sodium nitrite in aqueous solution in the sulphuric acid soln of p-aminophenol and carry out diazotization reaction, obtain Vandyke brown diazo liquid, with urea, thiocarbamide, thioether or mercaptan, destroy excessive Sodium Nitrite; (B) hydrolysis reaction: in reactor, add in advance dilute sulphuric acid, the above-mentioned diazo liquid of lower dropping that refluxes, reaction is hydrolyzed; (C) extracting and separating: hydrolyzed solution is after extracting Resorcinol, and water dilute sulphuric acid cover, for hydrolysis reaction, obtains Resorcinol crude product after extraction oil phase is sloughed solvent.Wherein in Resorcinol crude product, contained impurity has MEHQ, phenol, 2,4', and the materials such as 5-trihydroxy-biphenyl, 4,4' dihydroxy diphenyl, its foreign matter content is in 5% left and right.That this method has is low in the pollution of the environment, transformation efficiency and product yield is high, equipment corrosion is little, production cost is low and the easy advantage such as purification of product.Further, can adopt multiple post-treating method to produce Resorcinol sterling.The disclosed post-processing step of CN101412662B is: adopt the separation of nitrogen heating sublimation to obtain Resorcinol sterling, but the method is higher to the requirement of production process equipment, heavy industrialization is realized more difficult.
In addition, Shen Fazhi (see: p-aminophenol diazotization hydrolysis method is prepared Resorcinol. Guangdong chemical industry, 2010,37 (9): 56-57.) also reported that p-aminophenol diazotization hydrolysis method prepares the method for Resorcinol, wherein whole post-processing step comprises the processes such as precipitation (removing extraction solvent, lower same), distillation, decolouring, crystallization, separation.Concrete operations example is: first will extract oil reservoir intermediate water eccysis acid, then adopt 1% concentration NaHCO
3solution washing oil reservoir, to pH=5 left and right, then adopts rough vacuum (0.085MPa) and high vacuum (0.095MPa) order precipitation, rough vacuum precipitation 50%, the above precipitation of high vacuum approximately 40%.When liquid temperature reaches 80 ℃, changing decompression precipitation device is sublimation apparatus, vacuum tightness 5mmHg, and when liquid temperature reaches 170 ℃, discharging is very fast, continues slow heat temperature raising and makes normal discharging, 250 ℃ of still liquid final temperatures.The Resorcinol distilling out, through adding gac, zinc powder, is warming up to 80～85 ℃ of micro-reflux decolours, drips 30% sulfuric acid, then the 0.5～1h that refluxes, and gac is removed in separation while hot.Filtrate is lowered the temperature naturally, crystallization.Suction filtration obtains faint yellow Resorcinol, and containing wet 10% left and right, primary crystallization yield is 80%.In the faint yellow mother liquor that suction filtration obtains, still containing Resorcinol 5%～7%, can concentrate again and reclaim remaining Resorcinol product through extraction, precipitation, crystallization treatment etc., reclaim and increase yield 8% left and right, thus after aftertreatment total recovery in 88% left and right.In this post-processing step, adopt high vacuum precipitation, the problem such as must bring energy consumption to increase, operation easier is large, the rate of recovery of solvent can be very low like this; And the Resorcinol outward appearance obtaining after crystallization is faint yellow, do not obtain the Resorcinol xln of white needles, illustrate that product purity is not high.As far as we know, adopt sublimation process, will inevitably produce line clogging phenomenon, operation easier is larger.
Summary of the invention
The object of the invention is to, further improve p-aminophenol diazotization hydrolysis method and prepare the post-processing step of Resorcinol technique, the problem of the line clogging that solution employing distillation crystallization brings and the problem that energy consumption increases, operation easier is large that adopts high vacuum precipitation to bring.
The technical scheme of the improved post-treating method of the present invention is as follows.
P-aminophenol diazotization hydrolysis method is prepared a post-treating method for Resorcinol, comprises the steps:
(1) the extraction oil phase after reactive moieties extracting and separating and the extraction oil from step (6) extraction are merged, under nitrogen protection condition, precipitation is to finite concentration, and then slow cooling is to preset temp, and Resorcinol is crystallization in solvent;
(2) by after crystallization mixture separation, obtain crude product Resorcinol and crystalline mother solution;
(3) crude product Resorcinol is passed through to decolouring, separation, recrystallization, separation, dry, can obtain Resorcinol;
(4), through stripping, the Resorcinol in crystalline mother solution is transferred to the rear water layer of stripping;
(5) oil reservoir after reextraction, by precipitation, reclaims solvent, simultaneously by the residual discharge of still;
(6) merge strip rear water layer and recrystallization mother liquor, adopt recovery solvent to extract.
In above-mentioned steps (1), described precipitation concentration is 20%～60%, and preferred precipitation concentration is 30%～50%; Crystallization final temperature is 5～50 ℃, and preferably crystallization final temperature is 10～30 ℃; Described solvent can be methyl iso-butyl ketone (MIBK), methylethylketone, n-butyl acetate, propyl carbinol, vinyl acetic monomer or methyl tertiary butyl ether, preferable methyl isobutyl ketone or n-butyl acetate.
Separation method described in above-mentioned steps (2), (3) comprises centrifugation, separation, negative pressure leaching or settlement separate.Preferably under 0.03～0.1MPa vacuum tightness, carry out negative pressure leaching, more preferably negative pressure is 0.05～0.085MPa.
In above-mentioned steps (3), the described required material adding of decolouring operation is: one or more in gac, Sulfothiorine, Sodium Pyrosulfite, S-WAT, thiocarbamide, aluminium powder, zinc powder, iron powder, sulfuric acid, hydrochloric acid and nitric acid, the material preferably adding is the mixture of gac, Sodium Pyrosulfite, zinc powder and sulfuric acid.
In above-mentioned steps (3), described thermal separation temperature is controlled at 70～100 ℃, and preferably thermal separation temperature is 80～95 ℃; The crystallization concentration of recrystallization is 5%～60%, and preferably crystallization concentration is 25%～40%; 5～50 ℃ of recrystallization final temperatures, preferably recrystallization final temperature is 10～30 ℃; Separation temperature is controlled at 0～30 ℃, and preferably temperature is 5～25 ℃; Dry temperature is controlled at 50～85 ℃, and preferably temperature is 55～75 ℃, and wherein dry negative pressure is 0.08～0.1MPa.
In above-mentioned steps (4), described stripping process is exactly after raffinate water is mixed with above-mentioned filtrate, divides the reextraction that heats up for 3～4 times, and last layering obtains oil reservoir and water layer, and the recrystallization temperature of wherein stripping is 20～90 ℃, preferably 60～80 ℃.
In above-mentioned steps (5), it is 120～200 ℃ that described precipitation final temperature is controlled, preferably 140～170 ℃.
The quality of extraction solvent described in above-mentioned steps (6) is 1～5 times of water layer after stripping and recrystallization mother liquor total mass, preferably 2～3 times.
The advantage of post-treating method provided by the invention shows: flow process is simple, it is little to invest, without negative pressure pyroprocess, tar is few, energy consumption is low, yield is high, low to material purity requirement, without waste liquid generation, water and solvent cycle apply mechanically, quality product meets national standard, is easy to realization of industrialization.In addition, in the present invention, solvent and water have all obtained good recycle, reach zero-emission high-volume, have reduced production cost and environmental protection pressure; The present invention proposes solvent crystallization method, and the higher raw material of foreign matter content is conducive to purify; The present invention proposes anti-extraction process, has avoided decoking and has reclaimed Resorcinol operation, under hot conditions, directly the Resorcinol in crystalline mother solution is stripped to water layer, and impurity and solvent in oil reservoir adopts simple precipitation technique.
Accompanying drawing explanation
Fig. 1 is the process flow sheet that the preferred p-aminophenol diazotization of the present invention hydrolysis method is prepared the post-treating method of sterling Resorcinol technique.
The implication identifying in figure: DS1, DS2-precipitation; F1, F2, F3-separation; DC-decolouring; RC-recrystallization; D-dry; RE-reextraction; E-extraction.
Embodiment
Mode below in conjunction with drawings and Examples is further explained the present invention, but the present invention is not limited to these embodiment.Except as otherwise noted, " % " is wherein " quality % ".
The post-treating method that p-aminophenol diazotization hydrolysis method is prepared Resorcinol technique comprises the steps:
(1) the extraction oil phase after reactive moieties extracting and separating and the oil reservoir (i.e. extraction oil) from after step (6) extraction E are merged, under nitrogen protection condition, precipitation DS1 is to finite concentration, and then slow cooling is to preset temp, and Resorcinol is crystallization C in solvent;
(2) by after the separated F1 of crystallization mixture, obtain crude product Resorcinol and crystalline mother solution;
(3) crude product Resorcinol is passed through to decolouring DC, thermal separation F2, recrystallization RC, separated F3, dry D, can obtain Resorcinol;
(4), through reextraction RE, the Resorcinol in crystalline mother solution is transferred to the rear water layer of stripping;
(5) oil reservoir after reextraction, by precipitation DS2, reclaims solvent, simultaneously by the residual discharge of still;
(6) merge strip rear water layer and recrystallization mother liquor, adopt and reclaim solvent, extract E.
embodiment 1
(1) merge extraction oil phase (Resorcinol content is 3.5%, foreign matter content 0.39%) and the 480g extraction oil (Resorcinol content is 10.27%) of 800g reactive moieties, above-mentioned merging gained mixture 1280g, the wherein content 93% of methyl iso-butyl ketone (MIBK).Then under nitrogen protection condition, the concentration of normal pressure precipitation DS1 to 40%, then slow cooling to 25 ℃, make Resorcinol crystallization C in methyl iso-butyl ketone (MIBK), reclaims methyl iso-butyl ketone (MIBK) 963.6g and 23g precipitation recycle-water;
(2) by after the separated F1 of crystallization mixture, obtain the crude product Resorcinol of 49.5g and the crystalline mother solution of 254.8g;
(3) by adding the DC that decolours in 110g raffinate water, 1.5g gac, 0.6g Sodium Pyrosulfite, 0.1g zinc powder, 0.3g sulfuric acid in the crude product Resorcinol of 49.5g, be warming up to after 95 ℃ micro-backflow 1h; Then separated F2 while hot, hot water injection's filter cake with 15g, collect filtrate, with water-bath slow cooling to 56 ℃, now there is crystal to separate out, after insulation growing the grain 1h, after slow cooling to 25 ℃, carry out separated F3, by the frozen water flush cake of 20g, obtain Resorcinol that 32.7g is wet and the recrystallization mother liquor of 161.5g; Finally by product vacuum-drying D 2h, the Resorcinol of the 27.5g finally obtaining, appearance white, crystal formation is needle-like.By GB chemical titration, quality product is analyzed, changing minute content is 99.8%, and melting range is 172.5～173.2 ℃.
(4) merging 611.5g raffinate water and 23g precipitation recycle-water, under 80 ℃ of conditions, minute three reextraction RE 254.8g crystalline mother solutions, obtain the rear oil reservoir of 223g reextraction and the rear water layer of 666.3g reextraction, and the stripping rate of Resorcinol can reach 99.6%;
(5) oil reservoir after 223g reextraction is carried out to normal pressure precipitation DS2, obtain methyl iso-butyl ketone (MIBK) 210.1g, the residual 3.24g of still;
(6) water layer and 161.5g recrystallization mother liquor after 666.3g reextraction are merged, the methyl iso-butyl ketone (MIBK) that adopts 430g to reclaim, divides and four times mixed solution is extracted to E, and must extract oily 480g(Resorcinol content is 10.27%), raffinate water 777.8g, the percentage extraction of Resorcinol can reach 99.9%.Extraction oil jacket is used to precipitation DS1, and raffinate water jacket is with to RE and the DC that decolours of stripping.
Whole process Resorcinol yield is 98.4%, solvent recovering rate 98.6%.
embodiment 2～5
Adopt different reextraction temperature, other operational condition is with embodiment 1, and acquired results is as shown in table 1.
the impact of table 1 reextraction temperature on reextraction efficiency
embodiment 6
(1) (Resorcinol content is 3.5% to the extraction oil phase of merging 800g reactive moieties, assorted
Matter content 0.39%) and 545g extraction oil (Resorcinol content is 8.89%), above-mentioned merging gained mixture 1345g, the content 93.4% of n-butyl acetate in mixture.Then under nitrogen protection condition, the concentration of normal pressure precipitation DS1 to 35%, then slow cooling to 20 ℃, make Resorcinol crystallization C in n-butyl acetate, recovery of acetic acid positive butyl ester solvent 1056.8g and 34g precipitation recycle-water;
(2) by after the separated F1 of crystallization mixture, obtain the crude product Resorcinol of 52.7g and the crystalline mother solution of 232.1g;
(3) by adding the DC that decolours in 110g raffinate water, 1.5g gac, 0.6g Sulfothiorine, 0.1g zinc powder, 0.3g hydrochloric acid in the crude product Resorcinol of 52.7g, be warming up to after 95 ℃ micro-backflow 1h; Then separated F2 while hot, hot water injection's filter cake with 15g, collect filtrate, with water-bath slow cooling to 56 ℃, now there is crystal to separate out, after insulation growing the grain 1h, after slow cooling to 20 ℃, carry out separated F3, by the frozen water flush cake of 20g, obtain Resorcinol that 33.1g is wet and the recrystallization mother liquor of 163.5g; Finally by product vacuum-drying D 2h, the Resorcinol of the 27.9g finally obtaining, appearance white, crystal formation is needle-like.By GB chemical titration, quality product is analyzed, changing minute content is 99.5%, and melting range is 172.2～173.0 ℃.
(4) merging 612.2g raffinate water and 34g precipitation recycle-water, under 80 ℃ of conditions, minute three reextraction RE 232.1g crystalline mother solutions, obtain the rear oil reservoir of 217.0g reextraction and the rear water layer of 661.2g reextraction, and the stripping rate of Resorcinol can reach 99.4%;
(5) oil reservoir after 217.0g reextraction is carried out to normal pressure precipitation DS2, obtain n-butyl acetate solvent 187.6g, the residual 3.36g of still;
(6) water layer and 163.5g recrystallization mother liquor after 661.2g reextraction are merged, adopting 498.3g n-butyl acetate is solvent, divides and four times mixed solution is extracted to E, and must extract oily 545g(Resorcinol content is 8.89%), raffinate water 757.2g, the percentage extraction of Resorcinol can reach 99.3%.Extraction oil jacket is used to precipitation DS1, and raffinate water jacket is with to RE and the DC that decolours of stripping.
Whole process Resorcinol yield is 99.1%, solvent recovering rate 99.1%.
embodiment 7
(1) merge extraction oil phase (Resorcinol content is 3.4%, foreign matter content 0.85%) and the 476g extraction oil (Resorcinol content is 9.93%) of 800g reactive moieties, above-mentioned merging gained mixture 1276g, the content 92.5% of methyl iso-butyl ketone (MIBK) in mixture.Then under nitrogen protection condition, the concentration of normal pressure precipitation DS1 to 40%, then slow cooling to 10 ℃, make Resorcinol crystallization C in methyl iso-butyl ketone (MIBK), reclaims methyl iso-butyl ketone (MIBK) 1041.9g and 22.7g precipitation recycle-water;
(2) by after the separated F1 of crystallization mixture, obtain the crude product Resorcinol of 48.9g and the crystalline mother solution of 193.5g;
(3) by adding the DC that decolours in 110g raffinate water, 1.5g gac, 0.6g S-WAT, 0.1g zinc powder, 0.3g sulfuric acid in the crude product Resorcinol of 48.9g, be warming up to after 90 ℃ micro-backflow 1h; Then separated F2 while hot, hot water injection's filter cake with 15g, collect filtrate, with water-bath slow cooling to 56 ℃, now there is crystal to separate out, after insulation growing the grain 1h, after slow cooling to 25 ℃, carry out separated F3, by the frozen water flush cake of 20g, obtain Resorcinol that 32.4g is wet and the recrystallization mother liquor of 161.9g; Finally by product vacuum-drying D 2h, the Resorcinol of the 26.9g finally obtaining, appearance white, crystal formation is needle-like.By GB chemical titration, quality product is analyzed, changing minute content is 99.3%, and melting range is 172.7～173.4 ℃.
(4) merging 622.3g raffinate water and 22.7g precipitation recycle-water, under 80 ℃ of conditions, minute three reextraction RE 161.9g crystalline mother solutions, obtain the rear oil reservoir of 139.4g reextraction and the rear water layer of 667g reextraction, and the stripping rate of Resorcinol can reach 99.8%;
(5) oil reservoir after 139.4g reextraction is carried out to normal pressure precipitation DS2, obtain methyl iso-butyl ketone (MIBK) 125.4g, the residual 10.1g of still;
(6) water layer and 161.9g recrystallization mother liquor after 667g reextraction are merged, the methyl iso-butyl ketone (MIBK) that adopts 427.5g to reclaim, divides and four times mixed solution is extracted to E, and must extract oily 476g(Resorcinol content is 9.93%), raffinate water 780.3g, the percentage extraction of Resorcinol can reach 99.9%.Extraction oil jacket is used to precipitation DS1, and raffinate water jacket is with to RE and the DC that decolours of stripping.
Whole process Resorcinol yield is 98.2%, solvent recovering rate 98.9%.
Claims (17)
1. p-aminophenol diazotization hydrolysis method is prepared a post-treating method for Resorcinol, comprises the steps:
(1) the extraction oil phase after reactive moieties extracting and separating and the extraction oil from step (6) extraction are merged, under nitrogen protection condition, precipitation is to finite concentration, and then slow cooling is to preset temp, and Resorcinol is crystallization in solvent;
(2) by after crystallization mixture separation, obtain crude product Resorcinol and crystalline mother solution;
(3) by crude product Resorcinol by decolouring, thermal separation, recrystallization, separation, dry, can obtain Resorcinol;
(4), through stripping, the Resorcinol in crystalline mother solution is transferred to the rear water layer of stripping;
(5) oil reservoir after reextraction, by precipitation, reclaims solvent, simultaneously by the residual discharge of still;
(6) merge strip rear water layer and recrystallization mother liquor, adopt recovery solvent to extract;
Wherein, the precipitation concentration described in step (1) is 20%～60%, and crystallization final temperature is 5～50 ℃; Described in step (4), stripping is that raffinate water, precipitation recycle-water are mixed with crystalline mother solution, and described reextraction temperature is 20～90 ℃.
2. method according to claim 1, is characterized in that, the precipitation concentration described in step (1) is 30%～50%; Described crystallization final temperature is 10～30 ℃.
3. method according to claim 1, is characterized in that, described in step (1), solvent is methyl iso-butyl ketone (MIBK), methylethylketone, n-butyl acetate, propyl carbinol, vinyl acetic monomer or methyl tertiary butyl ether.
4. method according to claim 3, is characterized in that, described in step (1), solvent is methyl iso-butyl ketone (MIBK) or n-butyl acetate.
5. method according to claim 1, is characterized in that, the separation method described in step (2) and (3) is the negative pressure leaching under 0.03～0.1MPa vacuum tightness.
6. method according to claim 5, is characterized in that, the vacuum tightness described in step (2) and (3) is 0.05～0.085MPa.
7. method according to claim 1, it is characterized in that, the required material adding of decolouring operation described in step (3) is one or more in gac, Sulfothiorine, Sodium Pyrosulfite, S-WAT, zinc powder, iron powder, magnesium powder, sulfuric acid, hydrochloric acid.
8. method according to claim 7, is characterized in that, the mixture that the required material adding of decolouring operation described in step (3) is gac, Sodium Pyrosulfite, zinc powder and sulfuric acid.
9. method according to claim 1, is characterized in that, described in step (3), the crystallization concentration of recrystallization is 5%～60%; Recrystallization final temperature is 5～50 ℃.
10. method according to claim 9, is characterized in that, described in step (3), the crystallization concentration of recrystallization is 25%～40%; Recrystallization final temperature is 10～30 ℃.
11. methods according to claim 1, is characterized in that, described in step (3), thermal separation temperature is controlled at 70～100 ℃; Described dry temperature is controlled at 50～85 ℃, and dry negative pressure is 0.08～0.1MPa.
12. methods according to claim 11, is characterized in that, described in step (3), thermal separation temperature is controlled at 80～95 ℃; Described dry temperature is controlled at 55～75 ℃.
13. methods according to claim 1, is characterized in that, the temperature of stripping described in step (4) is 60～80 ℃.
14. methods according to claim 1, is characterized in that, it is 120～200 ℃ that precipitation final temperature described in step (5) is controlled.
15. methods according to claim 14, is characterized in that, it is 140～170 ℃ that precipitation final temperature described in step (5) is controlled.
16. methods according to claim 1, is characterized in that, the quality of extraction solvent described in step (6) is 1～5 times of water layer after stripping and recrystallization mother liquor total mass.
17. methods according to claim 16, is characterized in that, the quality of extraction solvent described in step (6) is 2～3 times of water layer after stripping and recrystallization mother liquor total mass.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862247A (en) * | 1970-03-04 | 1975-01-21 | Koppers Co Inc | Hydrolysis of para-aminophenol |
| CN101412662A (en) * | 2007-10-16 | 2009-04-22 | 江苏扬农化工集团有限公司 | Method for preparing p-dihydroxy benzene |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3862247A (en) * | 1970-03-04 | 1975-01-21 | Koppers Co Inc | Hydrolysis of para-aminophenol |
| CN101412662A (en) * | 2007-10-16 | 2009-04-22 | 江苏扬农化工集团有限公司 | Method for preparing p-dihydroxy benzene |
Non-Patent Citations (2)
| 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》.2010,第37卷(第9期), * |
| 祁晓静等.邻甲苯胺重氮化-水解制备邻甲酚工艺改进.《山西化工》.2009,第29卷(第6期), * |
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