CN104628527A - Hydroquinone preparation method - Google Patents
Hydroquinone preparation method Download PDFInfo
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- CN104628527A CN104628527A CN201310561012.7A CN201310561012A CN104628527A CN 104628527 A CN104628527 A CN 104628527A CN 201310561012 A CN201310561012 A CN 201310561012A CN 104628527 A CN104628527 A CN 104628527A
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- Prior art keywords
- chlorophenol
- para
- potassium hydroxide
- resorcinol
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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
- C07C37/02—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 halogen
Abstract
The present invention relates to a hydroquinone preparation method, especially to a method for preparing hydroquinone by adopting a supported solid alkali as a catalyst and carrying out an alkaline hydrolysis reaction on p-chlorophenol and a potassium hydroxide solution. According to the present invention, the supported solid alkali is adopted as the catalyst, the p-chlorophenol and the potassium hydroxide solution are subjected to an alkaline hydrolysis reaction at a certain temperature, the alkaline hydrolysis solution is filtered to recover the catalyst so as to be applied indiscriminately, the filtrate is acidified with hydrochloric acid to achieve the pH value of 2-3, the reaction product is extracted with methyl isobutyl ketone, and the raw material content and the product content in the raffinate are less than 0.05%.
Description
Technical field
The present invention relates to a kind of method preparing Resorcinol, particularly make catalyzer with load-type solid, para-chlorophenol and potassium hydroxide solution Basic fluxing raction prepare the method for Resorcinol.
Background technology
Resorcinol (Hydroquinone) is mainly as stopper, rubber antioxidant, azoic dyestuff, anthraquinone dye, stablizer, oxidation inhibitor etc. that the developer of taking a picture, medicine material, monomer transporting procedures add.
The production method of Resorcinol has more than ten to plant, and industrializedly at present mainly contains aniline oxidation style, diisopropylbenzene(DIPB) peroxidation method, dihydroxyphenyl propane method, phenol-hydrogen peroxide hydroxylation method.
Aniline oxidation style is Resorcinol production method the earliest.Production process generally includes two-step reaction, namely aniline is oxidized to para benzoquinone through Manganse Dioxide (or sodium dichromate 99) in sulfuric acid medium, in water, with iron powder, para benzoquinone is reduced into Resorcinol again, through concentrated, decolouring, crystallization, dry must Resorcinol finished product.In aniline, the total recovery about 85% of Resorcinol.This method has technical maturity, reaction easily control, yield and product purity advantages of higher.But raw material consumption is high, produce a large amount of manganous sulfates, sulphur waste liquor of ammonium and iron mud in process of production, environmental pollution is serious; The dilute sulphuric acid contained in reaction feed liquid is to equipment corrosion, and cost of equipment is high; In addition, promoter manganese recovery utilization rate is low.External this method superseded substantially.China produces Resorcinol from the 1950's, and its production method generally adopts aniline oxidation style.
For overcoming the deficiency that aniline oxidation style Resorcinol preparation technology exists, the present invention is to make load-type solid by oneself for catalyzer, adopt para-chlorophenol and potassium hydroxide alkaline hydrolysis operational path, alkali solution liquid filtering separation catalyst recovery is applied mechanically, and filtrate is separated and obtains Resorcinol after acidifying, solvent extraction.
Summary of the invention
The object of the invention is to solve the deficiency existed in existing aniline oxidation style Resorcinol preparation technology:
(1) complex process, facility investment is high;
(2) waste liquid in production process, waste residue amount are large;
(3) catalyst recovery utilization ratio is low, and production cost is high.
The invention provides a kind of homemade cheap, the method for catalyst preparing Resorcinol made by the solid alkali of Heat stability is good.By with the comparing of aniline oxidation style production technique, tool has the following advantages:
(1) technique is simple, and workable, facility investment is few;
(2) " three wastes " amount reduces greatly;
(3) catalyst stability is high, recovery is effective, and production cost is low.
The present invention adopts following technical scheme:
The present invention adopts load-type solid to make catalyzer, and para-chlorophenol and potassium hydroxide solution carry out Basic fluxing raction at a certain temperature; Alkali solution liquid reclaims catalyzer after filtration, applies mechanically; Filtrate with after hcl acidifying to pH=2 ~ 3, with methyl iso-butyl ketone (MIBK) extractive reaction product, the content <0.05% of raffinate Raw, product; Gained oil reservoir measures para-chlorophenol and Resorcinol content, calculates feed stock conversion, Resorcinol selectivity.
In technique scheme:
(1) in load type solid body base catalyst, carrier selects zirconium white, calcium oxide, titanium oxide, molecular sieve etc., preferential oxidation zirconium;
(2) presoma selects potassium hydroxide, sodium hydroxide, salt of wormwood, sodium carbonate, preferred potassium hydroxide, sodium hydroxide, calcines 4 hours after carrier loaded under 823K, and the special constant H in Hami can reach 26;
(3) potassium hydroxide solution concentration 5 ~ 50wt%, preferably 25 ~ 45wt%, more preferably 30 ~ 40wt%;
(4) para-chlorophenol and potassium hydroxide mol ratio are 1:1 ~ 20, preferred 1:3 ~ 10, more preferably 1:5 ~ 8;
(5) solid base catalyst and para-chlorophenol mass ratio are 1:1 ~ 30, preferred 1:5 ~ 20, more preferably 1:10 ~ 15;
(6) Basic fluxing raction temperature is 155 ~ 255 DEG C, preferably 185 ~ 235 DEG C, more preferably 195 ~ 215 DEG C;
(7) the Basic fluxing raction time is 4 ~ 20 hours, preferably 8 ~ 14 hours, more preferably 10 ~ 12 hours.
Following embodiment is intended to explanation and adds solid base catalyst and carry out catalysis para-chlorophenol alkaline hydrolysis and prepare Resorcinol, have catalytic activity high, consume low, feed stock conversion is high, selectivity of product is high, instead of limitation of the invention further.
Embodiment
Embodiment 1
Para-chlorophenol 106.6g, 40% concentration hydrogen potassium oxide 581.0g, KOH/ZrO is dropped in 1L autoclave
2catalyzer 10.7g, heats up after nitrogen replacement, and control temperature of reaction 215 DEG C, react 12 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 430g.Para-chlorophenol transformation efficiency 98.5%, Resorcinol selectivity 87.1%.
Comparative example 1
In 1L autoclave, drop into para-chlorophenol 106.6g, 40% concentration hydrogen potassium oxide 581.0g, heat up after nitrogen replacement, control temperature of reaction 215 DEG C, react 12 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 440g.Para-chlorophenol transformation efficiency 8.2%, Resorcinol selectivity 57.4%.
Embodiment 2
Para-chlorophenol 21.3g, 10% concentration hydrogen potassium oxide 493.9g, NaOH/ZrO is dropped in 1L autoclave
2catalyzer 3.0g, heats up after nitrogen replacement, and control temperature of reaction 210 DEG C, react 12 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 93.0g.Para-chlorophenol transformation efficiency 78.2%, Resorcinol selectivity 89.4%.
Embodiment 3
Para-chlorophenol 79.9g, 25% concentration hydrogen potassium oxide 522.9g, Na is dropped in 1L autoclave
2cO
3/ ZrO
2catalyzer 9.7g, heats up after nitrogen replacement, and control temperature of reaction 220 DEG C, react 8 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 245.3g.Para-chlorophenol transformation efficiency 82.4%, Resorcinol selectivity 90.1%.
Embodiment 4
Para-chlorophenol 101.1g, 35% concentration hydrogen potassium oxide 683.9g, K is dropped in 1L autoclave
2cO
3/ ZrO
2catalyzer 5.5g, heats up after nitrogen replacement, and control temperature of reaction 215 DEG C, react 12 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 447.5g.Para-chlorophenol transformation efficiency 71.6%, Resorcinol selectivity 86.3%.
Embodiment 5
Para-chlorophenol 111.9g, 45% concentration hydrogen potassium oxide 539.5g, K is dropped in 1L autoclave
2cO
3/ CaO catalyzer 5.0g, heats up after nitrogen replacement, and control temperature of reaction 220 DEG C, react 10 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 454.1g.Para-chlorophenol transformation efficiency 79.4%, Resorcinol selectivity 82.1%.
Embodiment 6
Para-chlorophenol 72.7g, 30% concentration hydrogen potassium oxide 581.0g, KOH/CaO catalyzer 21.4g is dropped in 1L autoclave, heat up after nitrogen replacement, control temperature of reaction 215 DEG C, react 12 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 325.6g.Para-chlorophenol transformation efficiency 88.6%, Resorcinol selectivity 86.3%.
Embodiment 7
Para-chlorophenol 85.2g, 32% concentration hydrogen potassium oxide 581.0g, K is dropped in 1L autoclave
2cO
3/ CaO catalyzer 8.5g, heats up after nitrogen replacement, and control temperature of reaction 185 DEG C, react 12 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 348.2g.Para-chlorophenol transformation efficiency 60.2%, Resorcinol selectivity 89.1%.
Embodiment 8
Para-chlorophenol 101.2g, 40% concentration hydrogen potassium oxide 551.0g, NaOH/ZrO is dropped in 1L autoclave
2catalyzer 15.2g, heats up after nitrogen replacement, and control temperature of reaction 235 DEG C, react 10 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 412.2g.Para-chlorophenol transformation efficiency 99.2%, Resorcinol selectivity 63.4%.
Embodiment 9
Para-chlorophenol 106.6g, 45% concentration hydrogen potassium oxide 516.0g, K is dropped in 1L autoclave
2cO
3/ ZrO
2catalyzer 12.7g, heats up after nitrogen replacement, and control temperature of reaction 215 DEG C, react 8 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 434.4g.Para-chlorophenol transformation efficiency 94.2%, Resorcinol selectivity 81.5%.
Embodiment 10
Para-chlorophenol 63.5g, 20% concentration hydrogen potassium oxide 581.0g, Na is dropped in 1L autoclave
2cO
3/ ZrO
2catalyzer 9.6g, heats up after nitrogen replacement, and control temperature of reaction 215 DEG C, react 16 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 218.4g.Para-chlorophenol transformation efficiency 77.5%, Resorcinol selectivity 89.2%.
Embodiment 11
Para-chlorophenol 106.6g, 40% concentration hydrogen potassium oxide 581.0g, KOH/ZrO is dropped in 1L autoclave
2catalyzer 10.7g, heats up after nitrogen replacement, and control temperature of reaction 215 DEG C, react 12 hours, alkali solution liquid reclaims catalyzer after filtration, and filtrate is acidified to pH=2 ~ 3 with 35% concentrated hydrochloric acid 430g.Para-chlorophenol transformation efficiency, Resorcinol selectivity, recovery after catalyst filtration, data are in table 1.
Data applied mechanically by table 1 catalyzer
| Apply mechanically number of times | Para-chlorophenol transformation efficiency (%) | Resorcinol selectivity (%) |
| 1 | 99.1 | 87.8 |
| 2 | 98.9 | 86.7 |
| 3 | 97.5 | 86.1 |
| 4 | 96.1 | 85.4 |
Claims (7)
1. prepare a method for Resorcinol, it is characterized in that, make catalyzer with load-type solid, para-chlorophenol and potassium hydroxide solution are carried out Basic fluxing raction; Alkali solution liquid reclaims catalyzer after filtering and applies mechanically; Filtrate, with after hcl acidifying to pH=2 ~ 3, obtains reaction product Resorcinol with methyl iso-butyl ketone (MIBK) extraction.
2. the method preparing Resorcinol according to claim 1, is characterized in that, in load type solid body base catalyst, carrier selects zirconium white, calcium oxide, titanium oxide, molecular sieve, and presoma selects potassium hydroxide, sodium hydroxide, salt of wormwood, sodium carbonate.
3. the method preparing Resorcinol according to claim 2, is characterized in that, calcines 4 hours after carrier loaded under 823K, and the special constant H in Hami reaches 26.
4. the method preparing Resorcinol according to claim 1, it is characterized in that, potassium hydroxide solution concentration is 5 ~ 50wt%, para-chlorophenol and potassium hydroxide mol ratio are 1:1 ~ 20, solid base catalyst and para-chlorophenol mass ratio are 1:1 ~ 30, Basic fluxing raction temperature is 155 ~ 255 DEG C, and the Basic fluxing raction time is 4 ~ 20 hours.
5. the method preparing Resorcinol according to claim 4, it is characterized in that, potassium hydroxide solution concentration is 25 ~ 45wt%, para-chlorophenol and potassium hydroxide mol ratio are 1:3 ~ 10, solid base catalyst and para-chlorophenol mass ratio are 1:5 ~ 20, Basic fluxing raction temperature is 185 ~ 235 DEG C, and the Basic fluxing raction time is 8 ~ 14 hours.
6. the method preparing Resorcinol according to claim 5, it is characterized in that, potassium hydroxide solution concentration 30 ~ 40wt%, para-chlorophenol and potassium hydroxide mol ratio are 1:5 ~ 8, solid base catalyst and para-chlorophenol mass ratio are 1:10 ~ 15, Basic fluxing raction temperature is 195 ~ 215 DEG C, and the Basic fluxing raction time is 10 ~ 12 hours.
7. the method preparing Resorcinol according to claim 1, is characterized in that, the content <0.05wt% of raffinate Raw, product.
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| CN201310561012.7A CN104628527B (en) | 2013-11-12 | 2013-11-12 | A kind of method preparing hydroquinone |
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| CN201310561012.7A CN104628527B (en) | 2013-11-12 | 2013-11-12 | A kind of method preparing hydroquinone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400447A (en) * | 2018-11-13 | 2019-03-01 | 科利生物科技（徐州）有限公司 | The preparation method of pyrogallol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2041592A (en) * | 1934-10-11 | 1936-05-19 | Pennsylvania Coal Products Com | Process of hydrolyzing chlor phenols |
| CN102675232A (en) * | 2012-05-17 | 2012-09-19 | 山东京博控股股份有限公司 | Synthetic method of 4-(6-chlorine-quinoxaline-2-yloxy)-phenol |
-
2013
- 2013-11-12 CN CN201310561012.7A patent/CN104628527B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2041592A (en) * | 1934-10-11 | 1936-05-19 | Pennsylvania Coal Products Com | Process of hydrolyzing chlor phenols |
| CN102675232A (en) * | 2012-05-17 | 2012-09-19 | 山东京博控股股份有限公司 | Synthetic method of 4-(6-chlorine-quinoxaline-2-yloxy)-phenol |
Non-Patent Citations (3)
| Title |
|---|
| 刘芳等: "负载型固体碱催化剂在有机合成中的研究进展", 《湖南科技学院学报》 * |
| 胡泰山等: "负载型固体碱KF/Al2O3在有机合成中的应用", 《精细石油化工》 * |
| 郑璐等: "电解对氯苯酚稀水溶液中脱氯降解机理研究", 《环境科学研究》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109400447A (en) * | 2018-11-13 | 2019-03-01 | 科利生物科技（徐州）有限公司 | The preparation method of pyrogallol |
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