CN1160703A - Production of catechol - Google Patents
Production of catechol Download PDFInfo
- Publication number
- CN1160703A CN1160703A CN96115184A CN96115184A CN1160703A CN 1160703 A CN1160703 A CN 1160703A CN 96115184 A CN96115184 A CN 96115184A CN 96115184 A CN96115184 A CN 96115184A CN 1160703 A CN1160703 A CN 1160703A
- Authority
- CN
- China
- Prior art keywords
- cyclohexanediol
- formic acid
- hydrogen peroxide
- pyrocatechol
- tetrahydrobenzene
- 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.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Catechol is produced through the processes of oxidizing cyclohexene by hydrogen peroxide solution in the presence of formic acid, direct neutralization by adding alkali and hydrolysis to produce 1,2-cyclohexane-diol, which is extracted with ethyl acetate and steamed to eliminate solvent to result in high-purity 1,2-cyclohexane-diol, leading the gasified and overheated 1,2-cyclohexane-diol solution steam into fixed bed with Ni-diatomite catalyst for catalytic dehydrogenation. Inactivated catalyst may be regenerated through the processes of steam cleaning, air oxidation, nitrogen blowing and hydrogen reduction, and repeatedly activated catalyst has total service life over 3,000 hr. The said production process has 1,2-cyclohexane-diol conversion rate as high as 98% and catechol yield over 85%.
Description
What the present invention relates to is to be the processing method of the production pyrocatechol of raw material by tetrahydrobenzene.
Pyrocatechol is important intermediate and a raw material of making Chemicals such as oxidation inhibitor, photographic developer, tanning agent, sterilant, spices, stopper, and many in the past is raw material production with orthodichlorobenzene, ortho chloro phenol.Modern age France sieve. it is that the oxidation style of raw material is produced pyrocatechol that Planck, all emerging product of Japanese space, Tokyo commerical test develop with phenol, improves that to pass by production stage many, seriously corroded, the shortcoming that cost is high.
Through 1, it is low, easy and simple to handle, the more economical method of a kind of raw materials cost that the 2-cyclohexanediol is produced pyrocatechol by tetrahydrobenzene.Its technology is by tetrahydrobenzene system 1,2-cyclohexanediol and make two steps of pyrocatechol with the catalytic dehydrogenation method again and form.Existing synthetic 1, in the technology of 2-cyclohexanediol, J.AM.CHEM.SOC.69, the methods of 2120 propositions are: under 40-45 ℃, with 13 moles of formic acid, 1 mole of hydrogen peroxide and 1 mole of tetrahydrobenzene reaction, react to finish to subtract to depress and steam except that adding the hydrolysis of 30%NaOH vlil behind a large amount of formic acid and the water, then use ethyl acetate extraction, through steaming desolventize 1,2-cyclohexanediol, yield 73%.Shortcomings such as its organic acid consumption is big, corrosion is strong, yield is low are obvious.Clear-227946 of Ri Tekai provides method to be: tetrahydrobenzene Peracetic Acid oxidation, reinforced mol ratio is 1: 1.2, reaction is complete isolates epoxy cyclohexane with distillation method, with big water gaging and Zeo-karb 70 ℃ of following hydrolysis, the concentration of this method gained cyclohexanediol is low, and has acetate to be difficult to defectives such as recovery and more difficult industrialization.By 1, the report of the screening of catalyst of 2-cyclohexanediol vapor catalytic dehydrogenation system pyrocatechol is more, as USSR (Union of Soviet Socialist Republics) " kinetics and catalysis " second phase in 1984 489 pages of detailed descriptions this respect Preparation of catalysts and screening, think and consider that from cost, selectivity and the regeneration possibility of catalyzer the Ni/ diatomite catalyzer of ni content about about 50% is optimal.16 pages of " refining of petroleum and petroleum chemistry " (Russia) 1985 1 phases provide on Ni/ diatomite catalyzer 1, processing condition such as the catalytic dehydrogenation of 2-cyclohexanediol produces that pyrocatechol is temperature required, flow rate of carrier gas, feed liquid air speed and water vapor consumption.Above-mentioned document is pointed out all that Ni/ diatomite activity of such catalysts prolonged with the reaction times and is successively decreased, need carry out frequent regeneration in order to recover its activity, therefore the reclaiming process of Ni/ diatomite catalyzer is by 1, and the 2-cyclohexanediol is produced one of key link of the whole process of pyrocatechol.But do not see that so far about 1,2-cyclohexanediol vapor catalytic dehydrogenation is produced the report of the concrete renovation process of all catalyzer of pyrocatechol (comprising Ni/ diatomite).
The purpose of this invention is to provide a kind of by tetrahydrobenzene through 1, the 2-cyclohexanediol is produced the renovation process of easy, the economic processing method, particularly catalyzer of pyrocatechol.
Processing condition provided by the invention and method are:
(1) synthesizes 1 by tetrahydrobenzene, the 2-cyclohexanediol
Stir and in the mixed solution of tetrahydrobenzene and formic acid, to drip hydrogen peroxide down or in the mixed solution of hydrogen peroxide and formic acid, to drip tetrahydrobenzene, insulated and stirred a few hours again after dripping, not stratified only to reaction solution.This moment, temperature of reaction was controlled at 25-70 ℃, was advisable with 30-50 ℃.Formic acid purity requirement 〉=85%, content of hydrogen peroxide in the hydrogen peroxide 〉=27.5%;
Under agitation directly add alkali, to point of equivalent or slightly be alkalescence, till the insulation reaction manthanoate saponification to the reaction solution fully.This moment, temperature was controlled at 20-60 ℃;
With organic solvent (as ethyl acetate) for several times at 40-45 ℃ of following extractive reaction liquid, then steam desolventize 1, the 2-cyclohexanediol; Extract the last aqueous solution through evaporation, crystallization, organic solvent extraction sodium formiate, use in the sulfuric acid again and recovery formic acid.
Tetrahydrobenzene in the raw materials, the mol ratio of formic acid and hydrogen peroxide is: tetrahydrobenzene: formic acid: hydrogen peroxide=1.0: 0.1-10.0: 0.1-5.0, with tetrahydrobenzene: formic acid: hydrogen peroxide=1.0: 0.5-1.0: 1.1-1.7 is advisable, the alkali add-on be with the formic acid equivalence ratio be 1.0-1.2: 1.0.Alkali can be used sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood.
(2) 1,2-cyclohexanediol catalytic dehydrogenation system pyrocatechols.
Catalyzer is to make with common pickling process, the precipitator method, and Ni content adds auxiliary agent with pickling process before the moulding and improved at the Ni/ of 45-55% diatom soil type, and adjuvant used is Na
2SO
4, SnCl
2, SnCl
4, K
2CO
3, K
2SO
4Deng, promoter metal content is 0.1-3.0%.Pack into after the moulding (column) in the fixed bed type reactor, use N
2Behind the cleaning air, under 400 ± 10 ℃, use H
2Can use behind the reduction activation 2-3h.With raw material 1, the 2-cyclohexanediol is made into the 5-30% aqueous solution, enters in the reactor through vaporizing, being superheated to temperature of reaction or being higher than temperature of reaction, and its air speed is 0.5-5.0/h (liquid hourly space velocity), and be 0.01-1 second duration of contact.Use N
2Be carrier gas, its air speed is 1000-5000/h, is advisable to be lower than 3000/h.Desorption temperature is 250-310 ℃ and is advisable with 280 ± 10 ℃.Reacted gas gets pyrocatechol through condensation separation.At 1 of the initial stage, the transformation efficiency of 2-cyclohexanediol is 100%, the yield 90% of pyrocatechol, and transformation efficiency and yield all descend to some extent behind the 30h, then can stop charging and carry out regeneration activating.Its schedule of operation is: do not lower the temperature down with 100-1500/h speed water flowing steam 1-2h in reactor, do not make its passivation to slough catalyst surface adsorbed organic matter and hydrogen: change blowing air or with N
2The air of dilution carries out oxidation, and the air air speed is 100-1500/h, and the time is 0.5-8h, is advisable with 1-3h; Change logical N again
23-5 minute, with cleaning free oxygen; Be warming up to 290-400 ℃ (being advisable) logical H with 300-360 ℃
2Reduction, air speed is 50-1000/h, about 1-5h finishes, also available N
2The H of dilution
2Reduction (H
2/ N
2Be 0.1-1.0), too fast to prevent reduction rate.The regeneration techniques of catalyzer of the present invention can make it use the accumulation life-span to reach more than the 3000h, and 1, the transformation efficiency of 2-cyclohexanediol and the average yield of pyrocatechol reach respectively more than 98% with more than 85%.
Characteristics of the present invention are: (1) cyclohexene oxide, neutralizing hydrolysis are carried out continuously, simplify many operations and raw material than prior art, and particularly the low of organic acid consumption also is comparatively outstanding.The inventive method make 1, the yield of 2-cyclohexanediol more than 98% and purity to reach more than 99% also be that present technology is incomparable.(2) benzene process can reclaim organic acid, and (3) 1,2-cyclohexanediol dehydrogenating technologies are reasonable, the particularly regeneration activating method practicality of catalyzer, effectively, even use 3000h, its 1, it is very considerable that the transformation efficiency of 2-cyclohexanediol reaches more than 98%.
Lift following example and proved the superior of the inventive method.1,2-cyclohexanediol yield is in tetrahydrobenzene; The pyrocatechol yield is with 1,2-cyclohexanediol meter:
Example 1
1L be equipped with formic acid that 20ml, content 88% are housed in the four-hole boiling flask of agitator, dropping funnel, reflux exchanger and thermometer and 140ml30% hydrogen peroxide, stir down, in 40 ± 2 ℃ drip the 100ml tetrahydrobenzene, drip finish stirring reaction to reaction solution not stratified till.Still control and add 38.72g Na under this temperature
2CO
3Be hydrolyzed, reaction solution shows slightly alkalescence and is thick.
Under 45 ℃, use 300ml ethyl acetate extraction hydrolyzed solution four times at every turn, combining extraction liquid, ethyl acetate is reclaimed in distillation, concentrates cooling, gets 1,2-cyclohexanediol 99.6g, purity 〉=99%, yield are 85%.
Example 2
The formic acid dosage is 30ml, and other raw material dosages and step such as example 1 get 1 at last, 2-cyclohexanediol 110.3g, and purity is 99%, yield 95%.
Example 3
The formic acid consumption is 60ml, and other get 1 with example 1,2-cyclohexanediol 110.0g, and purity is 99%, yield 93.8%.
Example 4
The hydrogen peroxide consumption is 120ml, and other get 1 with example 2,2-cyclohexanediol 105.5g, and purity 〉=99%, yield reaches 90%.
Example 5
Neutralization 77.44g Na
2CO
3, other are with example 1,1, and 2-cyclohexanediol yield reaches 93%.
Example 6
Oxidizing reaction temperature is 30 ℃, and other are with example 1,1, and 2-cyclohexanediol yield reaches 88%.
Example 7
Make the Ni/ diatomite catalyzer that column contains 2% tin, 50%Ni with pickling process, in fixed-bed reactor through 400 ℃, H
2Behind the reductase 12 h under 280 ℃, with N
2For carrier gas, air speed are 2000/h, with 1,2-cyclohexanediol 10% aqueous solution is raw material, vaporization, the overheated reactor that enters react, and the stock liquid hourly space velocity is 2/h, record 1 of reaction beginning 1h, the transformation efficiency of 2-cyclohexanediol is 100%, and the pyrocatechol yield is 90%.Record 1 behind the 30h, the transformation efficiency of 2-cyclohexanediol is 99.3%, and the pyrocatechol yield is 88.7%, stops charging.At 280 ℃ of following water flowing steam 1h, air speed is 1000/h, changes general N after the passivation
2Air (the N of dilution
2/ O
2Be 5), the air air speed is to change into behind the 1000/h oxidation 1h using N
2Purge catalyst surface about 5 minutes, and changed logical H again
2Reduction, air speed 800/h rises to 350 ℃ with temperature in the 1h simultaneously, logical H under this temperature
2Reduction 1h stops the hydrogen charging when being cooled to 280 ℃.Survey and use 1 of 30h for the second time, 2-cyclohexanediol transformation efficiency is 99,2%, and the pyrocatechol yield is 88.6%.So cyclic regeneration uses.Record when the catalyzer integral age reaches 3000h and use 1 after proceeding to 20h for the 116th time, 2-cyclohexanediol transformation efficiency is 98.1%, and the pyrocatechol yield is 86.5%.
Example 8
The catalyst regeneration reduction temperature is the highest 400 ℃, and other condition is with example 7.The catalyzer integral age reaches 1000h, records to use 1 behind the charging 20h for the 38th time, and the transformation efficiency of 2-cyclohexanediol is 98.7%, and the pyrocatechol yield is 85.3%.
Example 9
The oxidizing temperature of regenerated catalyst is 300 ℃, and other condition is with example 7, when the catalyzer integral age reaches 3000h, records and uses 1 behind the charging 20h for the 115th time, and the transformation efficiency of 2-cyclohexanediol is 98.5%, and the pyrocatechol yield is 88.6%.
Example 10
Ni-Sn/ diatomite catalyzer makes with the common precipitator method, with Na
2CO
3Be precipitation agent, other condition is with example 7.When the catalyzer integral age reaches 3000h, record 1 when using charging 19h the 118th time, the transformation efficiency of 2-cyclohexanediol is 98.3%, the yield of pyrocatechol is 87.6%.
Claims (5)
1, a kind of production method of pyrocatechol is in the presence of organic acid, uses the hydrogen peroxide oxidation tetrahydrobenzene, is hydrolyzed into 1 then, and the 2-cyclohexanediol becomes pyrocatechol through vapor catalytic dehydrogenation again, it is characterized by:
(1) synthesize 1, the 2-cyclohexanediol: with directly adding alkali neutralization, hydrolysis without separation behind the hydrogen peroxide oxidation tetrahydrobenzene, use 1 in the solvent extraction reaction solution again in the presence of formic acid, the 2-cyclohexanediol desolventizes the extraction liquid steaming and get; Institute adds the raw material tetrahydrobenzene, and the mol ratio of formic acid and hydrogen peroxide is:
Tetrahydrobenzene: formic acid: hydrogen peroxide=1.0: 0.1-10.0: the equivalence ratio of 0.1-5.0 alkali number and amount of formic acid is 1.0-1.2: 1.0, and reaction control temperature is oxidized to 25-70 ℃, neutralizes, is hydrolyzed to 20-60 ℃;
(2) catalytic dehydrogenation contains 1 of 5-30%, and the 2-cyclohexanediol aqueous solution is through the fixed-bed reactor of vaporizing, activated Ni/ diatomite catalyzer is equipped with in overheated feeding, and the feed liquid air speed is 0.5-5/h, and be 0.01-1 second duration of contact, simultaneously with N
2Be carrier gas, air speed is 1000-5000/h, and reaction control temperature 250-310 ℃, Ni content is 45-55% in the Ni/ diatomite catalyzer; The adding auxiliary agent is Na
2SO
4, SnCl
2, SnCl
4, K
2CO
3, K
2SO
4, its metal content is 0.1-3.0%; Catalyst activation condition: at 400 ± 10 ℃ of down logical H
22-3 hour.
2, the production method of pyrocatechol as claimed in claim 1 is characterized by and synthesizes 1, and in the 2-cyclohexanediol, its mol ratio that adds raw material tetrahydrobenzene, formic acid and hydrogen peroxide is:
Tetrahydrobenzene: formic acid: hydrogen peroxide=1.0: 0.5-1.0: 1.1-1.7 oxidizing reaction controlled temperature is 30-50 ℃; The catalytic dehydrogenating reaction controlled temperature is 280 ± 5 ℃, and the carrier gas air speed is 1000-5000/h.
3, the production method of pyrocatechol as claimed in claim 1 is characterized by and synthesizes 1, and described in the 2-cyclohexanediol technological process is to use ethyl acetate with solvent extraction, extracts 2-5 time down at 40-45 ℃; The aqueous solution after the extraction reclaims formate through evaporation, crystallization, organic solvent extraction, uses in the sulfuric acid again and recovery formic acid.
4, the production method of pyrocatechol as claimed in claim 1, it is characterized by describedly add alkali neutralization, hydrolysis is hydro-oxidation sodium, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood; The concentration of used formic acid 〉=85%; Hydrogen peroxide contains hydrogen peroxide 〉=27.5%.
5, the production method of pyrocatechol as claimed in claim 1 is characterized by after catalyzer uses inactivation and regenerates, and renovation process is: under the catalytic dehydrogenation temperature, using steam-treated 1-2h, air speed earlier is 100-1500/h: again with air or use N
2The atmospheric oxidation 0.5-8.0h of dilution, air speed is 100-1500/h; Then with N
2Purged 3-5 minute; Logical at last hydrogen reducing, 290-400 ℃ of temperature control, the time is 1-5h, H
2Air speed is 50-1000/h; Also available N
2The H of dilution
2Reduce H
2/ N
2=0.1-1.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115184A CN1160703A (en) | 1996-03-27 | 1996-03-27 | Production of catechol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115184A CN1160703A (en) | 1996-03-27 | 1996-03-27 | Production of catechol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1160703A true CN1160703A (en) | 1997-10-01 |
Family
ID=5122469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96115184A Pending CN1160703A (en) | 1996-03-27 | 1996-03-27 | Production of catechol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1160703A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101912781A (en) * | 2010-07-08 | 2010-12-15 | 南京工业大学 | Preparation method of dehydrogenation nickel-based/diatomite catalyst |
| CN103416236A (en) * | 2012-05-18 | 2013-12-04 | 无锡南村花卉苗木专业合作社 | Method for removing moss from leaves of bromeliaceae flowers |
| CN104069875A (en) * | 2013-03-28 | 2014-10-01 | 岳阳昌德化工实业有限公司 | Dehydrogenation catalyst, preparation method thereof, and dehydrogenation method |
| CN104072338A (en) * | 2013-03-28 | 2014-10-01 | 岳阳昌德化工实业有限公司 | Preparation method of o-dihydroxybenzene |
| CN108993615A (en) * | 2018-08-11 | 2018-12-14 | 四川蜀泰化工科技有限公司 | A kind of reduction of preparing hydrogen by reforming methanol copper-based catalysts, passivating method |
-
1996
- 1996-03-27 CN CN96115184A patent/CN1160703A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101912781A (en) * | 2010-07-08 | 2010-12-15 | 南京工业大学 | Preparation method of dehydrogenation nickel-based/diatomite catalyst |
| CN101912781B (en) * | 2010-07-08 | 2012-07-25 | 南京工业大学 | Preparation method of dehydrogenation nickel-based/diatomite catalyst |
| CN103416236A (en) * | 2012-05-18 | 2013-12-04 | 无锡南村花卉苗木专业合作社 | Method for removing moss from leaves of bromeliaceae flowers |
| CN104069875A (en) * | 2013-03-28 | 2014-10-01 | 岳阳昌德化工实业有限公司 | Dehydrogenation catalyst, preparation method thereof, and dehydrogenation method |
| CN104072338A (en) * | 2013-03-28 | 2014-10-01 | 岳阳昌德化工实业有限公司 | Preparation method of o-dihydroxybenzene |
| CN104072338B (en) * | 2013-03-28 | 2015-10-28 | 岳阳昌德化工实业有限公司 | A kind of method preparing pyrocatechol |
| CN104069875B (en) * | 2013-03-28 | 2016-08-03 | 岳阳昌德化工实业有限公司 | A kind of dehydrogenation and preparation method thereof and a kind of method of dehydrogenating |
| CN108993615A (en) * | 2018-08-11 | 2018-12-14 | 四川蜀泰化工科技有限公司 | A kind of reduction of preparing hydrogen by reforming methanol copper-based catalysts, passivating method |
| CN108993615B (en) * | 2018-08-11 | 2021-11-26 | 四川蜀泰化工科技有限公司 | Reduction and passivation method of copper-based catalyst for hydrogen production by methanol reforming |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5364987A (en) | Process for the preparation of 1,3-propanediol | |
| CA2073830C (en) | Continuous process for preparing dimethyl carbonate | |
| CN112299964B (en) | Preparation method of ethylene glycol monovinyl ether | |
| JPH05194291A (en) | Method of preparing 1,3-propanediol | |
| CN101774912A (en) | Technology for producing acetic ester | |
| JP2801381B2 (en) | Production method of high purity aniline | |
| JP2801358B2 (en) | Method for producing high-purity aniline | |
| UA119638C2 (en) | Integrated process for making acetic acid | |
| CN1160703A (en) | Production of catechol | |
| US4339604A (en) | Method for the preparation of cyclohexanol and/or cyclohexanone | |
| US4482767A (en) | Process for production of alcohols and LPG | |
| US2066496A (en) | Hydrogenation and dehydrogenation | |
| JPS584750A (en) | Preparation of high purity aniline | |
| US2437930A (en) | Production and recovery of olefin oxides | |
| CN110872208B (en) | Preparation method of cyclohexanol by coupling cyclohexane mixture dehydrogenation technology | |
| US5041682A (en) | Working up reaction mixtures containing cyclohexanol cyclohexanone and cyclohexyl hydroperoxide | |
| JP2819171B2 (en) | Method for producing aromatic alcohol | |
| JP3358631B2 (en) | Method for dehydrogenation of methanol | |
| Moiseev | Catalysis: 2000 Ad1 | |
| CN112010728A (en) | Alkali washing and water washing method | |
| US4035428A (en) | Process for production of orthophenylphenol | |
| JP2562150B2 (en) | Post-treatment method for reaction mixture containing cyclohexyl hydroperoxide | |
| Suzuki et al. | Oxidative methylation of toluene with methane over alkali metal bromide loaded rare earth oxides | |
| US4053524A (en) | Hydrogenation process and catalyst | |
| EP0004732B1 (en) | Preparation of 2-phenylethanol and 2-phenylethyl acetate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |