CN104059014A - Method for preparing carbazole through catalysis of diphenylamine - Google Patents
Method for preparing carbazole through catalysis of diphenylamine Download PDFInfo
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- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 34
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical class O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000498 cooling water Substances 0.000 claims abstract description 5
- 239000000284 extract Substances 0.000 claims abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical class 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 229910000314 transition metal oxide Chemical class 0.000 abstract 1
- 238000000605 extraction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- TWBPWBPGNQWFSJ-UHFFFAOYSA-N 2-phenylaniline Chemical group NC1=CC=CC=C1C1=CC=CC=C1 TWBPWBPGNQWFSJ-UHFFFAOYSA-N 0.000 description 1
- FNEHAOQZWPHONV-UHFFFAOYSA-N 9h-carbazole;sulfuric acid Chemical compound OS(O)(=O)=O.C1=CC=C2C3=CC=CC=C3NC2=C1 FNEHAOQZWPHONV-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002024 ethyl acetate extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Indole Compounds (AREA)
Abstract
本发明公开一种用二苯胺为原料催化合成制备咔唑的方法。本发明的方法是将催化剂颗粒填充到固定床反应器中加热至400-600℃，用100-200℃将二苯胺带入固定床反应器中进行反应，二苯胺与水体积比为1.0∶30，水蒸气流量10-50mL/min,进入固定床反应器进行反应，将从固定床中流出的高温蒸汽通入冷却水中，使反应物料溶于水中，用乙酸乙酯萃取出反应物料；所用的催化剂由碱金属的无机盐、五氧化二磷、过渡金属氧化物组成。本发明的咔唑制备方法制备过程简单易行，具有催化反应转化率高、无废液排放、制备成本低、清洁环保的优点。The invention discloses a method for catalytically synthesizing and preparing carbazole by using diphenylamine as a raw material. The method of the present invention is to fill the catalyst particles into a fixed-bed reactor and heat it to 400-600°C, and bring diphenylamine into the fixed-bed reactor at 100-200°C for reaction, and the volume ratio of diphenylamine to water is 1.0:30 , the water vapor flow rate is 10-50mL/min, enter the fixed bed reactor for reaction, pass the high temperature steam flowing out from the fixed bed into the cooling water, dissolve the reaction material in water, and extract the reaction material with ethyl acetate; The catalyst is composed of inorganic salts of alkali metals, phosphorus pentoxide and transition metal oxides. The carbazole preparation method of the invention has a simple and easy preparation process, and has the advantages of high conversion rate of catalytic reaction, no waste liquid discharge, low preparation cost, clean and environment-friendly.
Description
技术领域 technical field
本发明涉及咔唑的制备方法，特别是一种用二苯胺为原料催化合成制备咔唑的方法。 The invention relates to a method for preparing carbazole, in particular to a method for catalytically synthesizing and preparing carbazole by using diphenylamine as a raw material.
背景技术 Background technique
目前，咔唑在工业上是从煤焦油中提取。国内生产咔唑的方法是以粗蒽为原料，方法是硫酸萃取，形成硫酸咔唑盐溶液，然后用氨水反冲析出咔唑，参见：燃料与化工2013，44（6）37-40。该方法在一定程度上易产生大量工业废水。 At present, carbazole is extracted industrially from coal tar. The method of domestic production of carbazole is to use crude anthracene as the raw material. The method is sulfuric acid extraction to form a sulfuric acid carbazole salt solution, and then recoil with ammonia water to precipitate carbazole. See: Fuel and Chemical Industry 2013, 44 (6) 37-40. This method is easy to produce a large amount of industrial wastewater to a certain extent.
中国发明专利申请CN 101993411A公开一种合成咔唑的方法，该方法是用邻氨基联苯闭环脱氢，所用原料是氨或氯苯。这种方法的优点是原料易得，但其缺点是无市场竞争力，因为：(1) 合成路线长，反应步骤多。每步反应都需要复杂的前处理和后处理，分离设备和操作费用特别多。(2) 转化率低。大多数反应都伴有副反应，由于路线长，最终转化率低。(3) 废物处理量大，环保费用高。 Chinese invention patent application CN 101993411A discloses a method for synthesizing carbazole, which uses o-aminobiphenyl ring-closed dehydrogenation, and the raw material used is ammonia or chlorobenzene. The advantage of this method is that the raw materials are easy to obtain, but its disadvantage is that it has no market competitiveness because: (1) The synthetic route is long and there are many reaction steps. Each step of the reaction requires complex pre-treatment and post-treatment, and the separation equipment and operation costs are particularly high. (2) The conversion rate is low. Most of the reactions are accompanied by side reactions, and the final conversion is low due to the long route. (3) The amount of waste to be treated is large, and the cost of environmental protection is high.
传统方法用二苯胺合成咔唑，所用的催化剂体系为Pd, Pt,均相或非均相合成，参见：精细与专用化学品2012，20（2）8-12；Synthesis, 2007, (13), 2055-2059；European Journal of Organic Chemistry, 2009,(27), 4614-4621。其催化剂用到的载体有Al2O3,MgO等或无载体；溶剂有水，氯仿，DMF等；临氢和加压条件。但这些催化剂的缺点是都需使用贵金属元素，并存在着贵金属难于分离和难于回收的不足。 The traditional method uses diphenylamine to synthesize carbazole, the catalyst system used is Pd, Pt, homogeneous or heterogeneous synthesis, see: Fine and Specialty Chemicals 2012, 20 (2) 8-12; Synthesis, 2007, (13) , 2055-2059; European Journal of Organic Chemistry, 2009, (27), 4614-4621. The carrier used in the catalyst includes Al 2 O 3 , MgO, etc. or no carrier; the solvent includes water, chloroform, DMF, etc.; hydrogen and pressurized conditions. However, the disadvantages of these catalysts are that they all need to use noble metal elements, and there are disadvantages that noble metals are difficult to separate and recover.
发明内容 Contents of the invention
本发明为一种可克服现有技术不足，反应工艺简单的用二苯胺催化制备咔唑方法。 The invention is a method for preparing carbazole by catalyzing diphenylamine, which can overcome the shortcomings of the prior art and has a simple reaction process.
本发明的用二苯胺催化制备咔唑的方法是将催化剂颗粒填充到固定床反应器中加热至400-600℃，用100-200℃将二苯胺带入固定床反应器中进行反应，二苯胺与水体积比为1.0∶30，水蒸气流量10-50mL/min,进入固定床反应器进行反应，将从固定床中流出的高温蒸汽通入冷却水中，使反应物料溶于水中，用乙酸乙酯萃取出反应物料；所用的催化剂制备方法是：称取3.40 g五氧化二钒、2g 硝酸铁、3g硝酸镍、1.2g五氧化二磷、2.4g钼酸铵、2.0g硝酸铋和1g氯化钾加入100mL草酸水溶液中，在60-90oC温度下搅拌溶解，并加入80-95g的γ-Al2O3剂载体浸渍，将前述浸渍后的催化剂在100℃-200℃充分干燥，然后于400℃-800℃下焙烧5-20小时，筛分为大小约30目的颗粒，得到本发明使用的催化剂。 The method for preparing carbazole with diphenylamine catalysis of the present invention is to fill catalyst particles into a fixed-bed reactor and heat to 400-600°C, and bring diphenylamine into the fixed-bed reactor at 100-200°C for reaction. The volume ratio to water is 1.0:30, the steam flow rate is 10-50mL/min, enter the fixed bed reactor for reaction, pass the high temperature steam flowing out from the fixed bed into the cooling water, dissolve the reaction materials in water, and use ethyl acetate The ester extracts the reaction material; the catalyst preparation method used is: weigh 3.40 g vanadium pentoxide, 2 g ferric nitrate, 3 g nickel nitrate, 1.2 g phosphorus pentoxide, 2.4 g ammonium molybdate, 2.0 g bismuth nitrate and 1 g chlorine Add potassium chloride into 100mL oxalic acid aqueous solution, stir and dissolve at 60-90 ° C, add 80-95g of γ-Al 2 O to impregnate the carrier, fully dry the impregnated catalyst at 100°C-200° C , Then bake at 400°C-800°C for 5-20 hours, sieve into particles with a size of about 30 mesh, and obtain the catalyst used in the present invention.
本发明的咔唑制备方法制备过程简单易行，且在制备过程中不产生污染，而且催化剂不使用稀贵金属，具有催化反应转化率高、无废液排放、制备成本低、清洁环保的优点。 The preparation method of the carbazole of the present invention has a simple and easy preparation process, does not generate pollution during the preparation process, and does not use rare and precious metals as a catalyst, and has the advantages of high conversion rate of catalytic reaction, no waste liquid discharge, low preparation cost, clean and environment-friendly.
具体实施方式 Detailed ways
本发明的具体方案如下： Concrete scheme of the present invention is as follows:
1、催化剂的制备工艺如下： 1. The catalyst preparation process is as follows:
3.40 g五氧化二钒、2g 硝酸铁、3g硝酸镍、1.2g五氧化二磷、2.4g钼酸铵、2.0g硝酸铋和1g氯化钾将前述各物质加入100mL的质量浓度10%的草酸水溶液中，在60-90oC温度下搅拌溶解，再加入80-95g的γ-Al2O3催化剂载体浸渍，筛分出大小约30目的颗粒。本发明的催化剂大小在30目左右有利于在固定床中催化反应。 3.40 g vanadium pentoxide, 2 g ferric nitrate, 3 g nickel nitrate, 1.2 g phosphorus pentoxide, 2.4 g ammonium molybdate, 2.0 g bismuth nitrate and 1 g potassium chloride. Add the aforementioned substances to 100 mL of 10% oxalic acid In the aqueous solution, stir and dissolve at a temperature of 60-90 o C, then add 80-95g of gamma-Al 2 O 3 catalyst carrier for impregnation, and sieve out particles with a size of about 30 mesh. The size of the catalyst of the present invention is about 30 meshes, which is favorable for catalytic reaction in a fixed bed.
2、利用二苯胺为原料催化合成咔唑的工艺如下： 2. Utilize diphenylamine as the process of raw material catalytic synthesis of carbazole as follows:
1）将30目粒度的催化剂颗粒填充到管径为10 mm，管长250 mm的固定床反应器中，并加热至400-600℃。 1) Fill the catalyst particles with a particle size of 30 mesh into a fixed-bed reactor with a pipe diameter of 10 mm and a pipe length of 250 mm, and heat it to 400-600 °C.
2）二苯胺与水体积比为1.0∶30配成混合溶液，经过预热至90-100℃。 2) The volume ratio of diphenylamine and water is 1.0:30 to form a mixed solution, which is preheated to 90-100°C.
3）通过150℃的高温水蒸气，利用柱塞泵将上述90-100℃的预热混合液带入预热器中，预热至100-200℃，后带入固定床反应器中，流量10-50mL/min。 3) Through the high-temperature water vapor of 150°C, the above-mentioned preheated mixed liquid of 90-100°C is brought into the preheater by the plunger pump, preheated to 100-200°C, and then brought into the fixed-bed reactor, the flow rate 10-50mL/min.
4）固定床反应温度为400-600℃。 4) The fixed bed reaction temperature is 400-600°C.
5）将从固定床中流出的高温蒸汽通入冷却水中，使反应物料溶于水中，用乙酸乙酯萃取出反应物料，用气相色谱跟踪监测原料转化率及反应物产率。 5) Pass the high-temperature steam flowing out of the fixed bed into the cooling water to dissolve the reaction materials in water, extract the reaction materials with ethyl acetate, and track and monitor the conversion rate of raw materials and the yield of reactants with gas chromatography.
6）萃取分离出的水溶液返回继续用于加热成蒸汽，带原料二苯胺。 6) The aqueous solution separated by extraction is returned to continue to be heated into steam, with raw material diphenylamine.
以下是本发明的一个实施例： The following is an embodiment of the present invention:
将30目粒度的催化剂颗粒填满管径为10 mm，管长250 mm的固定床反应器中，并加热至530℃。将1.7g二苯胺与50mL水配成混合溶液，预热至100℃。用150℃的高温水蒸气，利用柱塞泵将上述100℃的预热混合液带入预热器中，预热至190℃，后带入固定床反应器中，蒸汽流量40mL/min。将从固定床中流出的高温蒸汽通入冷却水中，使反应物料溶于水中，用乙酸乙酯萃取出反应物料，用气相色谱跟踪监测原料转化率为91%，产品咔唑选择性为92%。萃取分离出的水溶液返回继续用于加热成150℃蒸汽，带原料二苯胺。乙酸乙酯萃取液经分离提纯可得咔唑产品1.4g。产品收率约为：82%。 Fill the catalyst particles with a particle size of 30 mesh into a fixed-bed reactor with a pipe diameter of 10 mm and a pipe length of 250 mm, and heat it to 530 °C. Prepare a mixed solution of 1.7g diphenylamine and 50mL water, and preheat to 100°C. Use 150°C high-temperature steam to bring the above-mentioned 100°C preheated mixture into the preheater with a plunger pump, preheat to 190°C, and then bring it into the fixed-bed reactor with a steam flow rate of 40mL/min. Pass the high-temperature steam flowing out of the fixed bed into cooling water, dissolve the reaction materials in water, extract the reaction materials with ethyl acetate, track and monitor the conversion rate of raw materials with gas chromatography, and the conversion rate of raw materials is 91%, and the selectivity of product carbazole is 92%. . The aqueous solution separated by extraction is returned and continued to be heated into steam at 150°C, with raw material diphenylamine. The ethyl acetate extract was separated and purified to obtain 1.4 g of carbazole product. Product yield is about: 82%.
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Cited By (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 |
| CN116803498A (en) * | 2023-06-13 | 2023-09-26 | 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 |
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|---|---|---|---|---|
| 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 |
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| 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 |
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| MIROSLAV VLČKO，等: "Dehydrocyclization of Diphenylamine to Carbazole over Platinum-Based Bimetallic Catalysts", 《CHINESE JOURNAL OF CATALYSIS》, vol. 31, no. 12, 31 December 2010 (2010-12-31), pages 1439 - 1444, XP027565108 * |
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Cited By (3)
| 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 |
| CN116803498A (en) * | 2023-06-13 | 2023-09-26 | 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 |
| 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 |
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