CN104059014B - A kind of method that carbazole is prepared in diphenylamines catalysis - Google Patents
A kind of method that carbazole is prepared in diphenylamines catalysis Download PDFInfo
- Publication number
- CN104059014B CN104059014B CN201410292101.0A CN201410292101A CN104059014B CN 104059014 B CN104059014 B CN 104059014B CN 201410292101 A CN201410292101 A CN 201410292101A CN 104059014 B CN104059014 B CN 104059014B
- Authority
- CN
- China
- Prior art keywords
- diphenylamines
- fixed bed
- bed reactors
- carbazole
- catalyst
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
Abstract
A kind of diphenylamines of disclosure is the method for the synthetically prepared carbazole of catalytic material.The method of the present invention is to be filled in fixed bed reactors by catalyst granules to heat to 400-600 DEG C, with 100-200 DEG C diphenylamines brought in fixed bed reactors and react, diphenylamines and water volume ratio are 1.0: 30, vapor flow 10-50mL/min, entrance fixed bed reactors react, the high-temperature steam flowed out from fixing bed is passed in cooling water, make reaction mass soluble in water, be extracted with ethyl acetate out reaction mass；Catalyst used is made up of alkali-metal inorganic salt, phosphorus pentoxide, transition metal oxide.The carbazole preparation method preparation process of the present invention is simple, has that catalytic reaction conversion ratio is high, low without discharging of waste liquid, preparation cost, the advantage of clean environment firendly.
Description
Technical field
The preparation method that the present invention relates to carbazole, particularly a kind of diphenylamines are the method for the synthetically prepared carbazole of catalytic material.
Background technology
At present, carbazole is industrially extract from coal tar.The method of domestic production carbazole is with crude anthracene for raw material, and method is that sulphuric acid extracts, and forms sulfuric acid carbazole saline solution, then precipitates out carbazole with ammonia recoil, referring to: fuel and chemical industry 2013,44(6) 37-40.The method is easily generated a large amount of industrial wastewater to a certain extent.
Chinese invention patent application CN101993411A discloses a kind of method synthesizing carbazole, and the method is to use o-aminobiphenyl closed loop dehydrogenation, and raw materials used is ammonia or chlorobenzene.The advantage of this method is that raw material is easy to get, but its shortcoming is without the market competitiveness, because: (1) synthetic route is long, and reactions steps is many.Often step reaction be required for complexity pre-treatment and post processing, separation equipment and operating cost many especially.(2) low conversion rate.Great majority reaction is all with side reaction, owing to route is long, and final low conversion rate.(3) waste throughput is big, and expenses of environmental protection is high.
Traditional method diphenylamines synthesizes carbazole, and catalyst system used is Pd, Pt, homogeneous or heterogeneous synthesis, referring to: fine and specialty chemicals 2012,20(2) 8-12；Synthesis, 2007, (13), 2055-2059；EuropeanJournalofOrganicChemistry, 2009, (27), 4614-4621.The carrier that its catalyst is used has Al2O3, MgO etc. or carrier-free；Solvent has water, chloroform, DMF etc.；Face hydrogen and pressurized conditions.But the shortcoming of these catalyst is all to need to use precious metal element, and there is the deficiency that noble metal is difficult to separate and be difficult to reclaim.
Summary of the invention
The present invention is that one can overcome prior art not enough, and reaction process simply prepares carbazole Method with diphenylamines catalysis.
The present invention to prepare the method for carbazole with diphenylamines catalysis be filled in fixed bed reactors by catalyst granules to heat to 400-600 DEG C, with 100-200 DEG C diphenylamines brought in fixed bed reactors and react, diphenylamines and water volume ratio are 1.0: 30, vapor flow 10-50mL/min, entrance fixed bed reactors react, the high-temperature steam flowed out from fixing bed is passed in cooling water, make reaction mass soluble in water, be extracted with ethyl acetate out reaction mass；Method for preparing catalyst used is: weighs 3.40g vanadic anhydride, 2g ferric nitrate, 3g nickel nitrate, 1.2g phosphorus pentoxide, 2.4g ammonium molybdate, 2.0g bismuth nitrate and 1g potassium chloride and adds in 100mL oxalic acid aqueous solution, at 60-90oStirring and dissolving at C temperature, and add the γ-Al of 80-95g2O3Agent carrier impregnates, and the catalyst after aforementioned impregnation is fully dry at 100 DEG C-200 DEG C, then roasting 5-20 hour at 400 DEG C-800 DEG C, and the granule of about 30 orders sized by screening obtains the catalyst that the present invention uses.
The carbazole preparation method preparation process of the present invention is simple, and does not produce to pollute in preparation process, and catalyst does not use rare precious metal, has that catalytic reaction conversion ratio is high, low without discharging of waste liquid, preparation cost, the advantage of clean environment firendly.
Detailed description of the invention
The concrete scheme of the present invention is as follows:
1, the preparation technology of catalyst is as follows:
Aforementioned each material is added in the oxalic acid aqueous solution of the mass concentration 10% of 100mL by 3.40g vanadic anhydride, 2g ferric nitrate, 3g nickel nitrate, 1.2g phosphorus pentoxide, 2.4g ammonium molybdate, 2.0g bismuth nitrate and 1g potassium chloride, at 60-90oStirring and dissolving at C temperature, adds the γ-Al of 80-95g2O3Impregnation of catalyst carriers, screens out the granule of size about 30 order.The catalyst size of the present invention is conducive to catalytic reaction in fixing bed about 30 orders.
2, utilize the technique that diphenylamines synthesizes carbazole for catalytic material as follows:
1) catalyst granules of 30 order granularities being filled into caliber is 10mm, in the fixed bed reactors of pipe range 250mm, and heats to 400-600 DEG C.
2) diphenylamines and water volume ratio are be made into mixed solution at 1.0: 30, through being preheated to 90-100 DEG C.
3) by the high-temperature vapor of 150 DEG C, utilize plunger displacement pump to bring in preheater by the preheating mixed liquor of above-mentioned 90-100 DEG C, be preheated to 100-200 DEG C, after bring in fixed bed reactors, flow 10-50mL/min.
4) fixed bed reaction temperature is 400-600 DEG C.
5) high-temperature steam flowed out from fixing bed is passed in cooling water, make reaction mass soluble in water, be extracted with ethyl acetate out reaction mass, with gas chromatogram tracking and monitoring feed stock conversion and reactant productivity.
6) aqueous solution that extract and separate goes out returns and continues on for being heated into steam, carrying raw material diphenylamines.
The following is one embodiment of the present of invention:
The catalyst granules of 30 order granularities is filled up caliber is 10mm, in the fixed bed reactors of pipe range 250mm, and heats to 530 DEG C.1.7g diphenylamines and 50mL water are made into mixed solution, are preheated to 100 DEG C.With the high-temperature vapor of 150 DEG C, utilize plunger displacement pump to bring in preheater by the preheating mixed liquor of above-mentioned 100 DEG C, be preheated to 190 DEG C, after bring in fixed bed reactors, steam flow 40mL/min.Being passed into by the high-temperature steam flowed out from fixing bed in cooling water, make reaction mass soluble in water, be extracted with ethyl acetate out reaction mass, be 91% with gas chromatogram tracking and monitoring feed stock conversion, product carbazole selectivity is 92%.The aqueous solution that extract and separate goes out returns and continues on for being heated into 150 DEG C of steam, carrying raw material diphenylamines.The separated purification of acetic acid ethyl acetate extract can obtain carbazole product 1.4g.Product yield is about: 82%.
Claims (1)
1. the method preparing carbazole with diphenylamines catalysis, it is characterized in that being filled in fixed bed reactors by catalyst granules heats to 400-600 DEG C, with 100-200 DEG C diphenylamines brought in fixed bed reactors and react, diphenylamines and water volume ratio are 1.0: 30, vapor flow 10-50mL/min, enters fixed bed reactors and reacts, and is passed into by the high-temperature steam flowed out in cooling water from fixing bed, make reaction mass soluble in water, be extracted with ethyl acetate out reaction mass；Method for preparing catalyst used is: weighs 3.40g vanadic anhydride, 2g ferric nitrate, 3g nickel nitrate, 1.2g phosphorus pentoxide, 2.4g ammonium molybdate, 2.0g bismuth nitrate and 1g potassium chloride and adds in 100mL oxalic acid aqueous solution, at 60-90oStirring and dissolving at C temperature, and add the γ-Al of 80-95g2O3Agent carrier impregnates, and the catalyst after aforementioned impregnation is fully dry at 100 DEG C-200 DEG C, and then roasting 5-20 hour at 400 DEG C-800 DEG C, is the granule of 30 orders sized by screening, obtains the catalyst that the present invention uses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410292101.0A CN104059014B (en) | 2014-06-26 | 2014-06-26 | A kind of method that carbazole is prepared in diphenylamines catalysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410292101.0A CN104059014B (en) | 2014-06-26 | 2014-06-26 | A kind of method that carbazole is prepared in diphenylamines catalysis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104059014A CN104059014A (en) | 2014-09-24 |
| CN104059014B true CN104059014B (en) | 2016-06-29 |
Family
ID=51546983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410292101.0A Expired - Fee Related CN104059014B (en) | 2014-06-26 | 2014-06-26 | A kind of method that carbazole is prepared in diphenylamines catalysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104059014B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115215784A (en) * | 2021-09-16 | 2022-10-21 | 山西紫罗蓝新材料科技有限公司 | Synthetic process for synthesizing carbazole |
| CN116803498B (en) * | 2023-06-13 | 2024-02-13 | 北京海望氢能科技有限公司 | Dehydrogenation catalyst, preparation method and application thereof in preparation of carbazole through diphenylamine dehydrogenation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5760247A (en) * | 1996-05-24 | 1998-06-02 | Bayer Aktiengesellschaft | Process for the preparation of carbazole |
| US5856516A (en) * | 1996-08-21 | 1999-01-05 | Bayer Aktiengesellschaft | Process for the preparation of carbazole |
| CN103772267A (en) * | 2012-10-24 | 2014-05-07 | 常州化学研究所 | Method for preparing carbazole from diphenylamine |
-
2014
- 2014-06-26 CN CN201410292101.0A patent/CN104059014B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5760247A (en) * | 1996-05-24 | 1998-06-02 | Bayer Aktiengesellschaft | Process for the preparation of carbazole |
| US5856516A (en) * | 1996-08-21 | 1999-01-05 | Bayer Aktiengesellschaft | Process for the preparation of carbazole |
| CN103772267A (en) * | 2012-10-24 | 2014-05-07 | 常州化学研究所 | Method for preparing carbazole from diphenylamine |
Non-Patent Citations (2)
| Title |
|---|
| Dehydrocyclization of Diphenylamine to Carbazole over Platinum-Based Bimetallic Catalysts;Miroslav VLČKO，等;《Chinese Journal of Catalysis》;20101231;第31卷(第12期);第1439-1444页 * |
| 催化合成咔唑的研究进展;侯启军，等;《精细与专用化学品》;20120229;第20卷(第2期);第8-12页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104059014A (en) | 2014-09-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cantillo et al. | In situ generated iron oxide nanocrystals as efficient and selective catalysts for the reduction of nitroarenes using a continuous flow method | |
| CN103224465B (en) | 2,2,6,6,-tetramethyl-4-piperidone continuous synthesis method | |
| CN104059014B (en) | A kind of method that carbazole is prepared in diphenylamines catalysis | |
| CN101492457B (en) | Method of preparing hydronol | |
| CN103864624A (en) | Simple method for efficiently preparing secondary amine through alkali catalyzed N-alkylation | |
| CN103694169B (en) | Micro passage reaction is utilized to synthesize the method for 2,2,4-trimethylammonium-1,2-dihydroquinoline and polymkeric substance thereof | |
| CN104387340A (en) | Method for preparing N-methyl piperazine and catalyst of N-methyl piperazine | |
| CN101906057A (en) | Method for preparing CLT acid (6-chloro-3-aminotoluene-4-sulfoacid) by utilizing o-chlorotoluene direct nitrification method | |
| CN104892426A (en) | Method for preparing 1-nitroanthraquinone by using pyrrolidinone ionic liquid as catalyst | |
| CN111018681B (en) | Method for preparing benzoin in micro-reaction device | |
| CN103113240A (en) | Process for directly synthesizing p-aminophenol through hydrogenation of nitrobenzene | |
| CN107814691B (en) | Method for synthesizing ethylguaiacol | |
| CN104043467B (en) | A kind of catalyst for the preparation of carbazole and preparation method | |
| CN104326940A (en) | Method for synthesizing 2,6-dichlorobenzonitrile by ammoxidation | |
| CN103880717B (en) | The preparation method of two (3-allyl group-4-hydroxy phenyl) sulfones and derivative thereof | |
| CN104276928B (en) | The preparation method of two [1-(4-hydroxy phenyl)-1-the methylethyl]-Resorcinol of a kind of 4,6- | |
| CN109400482B (en) | Method for preparing p-nitrotoluene by toluene nitration | |
| CN103880694A (en) | Preparation method of 2-hydroxy-5-aminobenzoic acid | |
| CN104418746A (en) | Method for preparing diphenyl m-phthalate through micro-channel reaction apparatus | |
| CN105753716A (en) | Method for preparing arylamine by reducing aromatic nitro compound | |
| CN101921178B (en) | Method for preparing methylphenol from methylbenzene by one-step hydroxylation | |
| CN103739571A (en) | Synthesis method of phenyl glycidyl ether | |
| CN104262247B (en) | A kind of synthetic method of 2,6-diamino-3,5-di nitryl pyridine-1-oxide | |
| CN105418358A (en) | Method for preparing o-chlorotoluene | |
| CN102951994A (en) | Method for producing 2,6-dichlorotoluene and 2,3-dichlorotoluene by utilizing 2-chlorotoluene to directionally chloridize |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160629 Termination date: 20200626 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |