CN104043467B - A kind of catalyst for the preparation of carbazole and preparation method - Google Patents
A kind of catalyst for the preparation of carbazole and preparation method 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 44
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 20
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 10
- 229910000314 transition metal oxide Chemical class 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052720 vanadium Inorganic materials 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 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 claims description 3
- 238000005470 impregnation Methods 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- -1 transition metal salt Chemical class 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 3
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 239000010970 precious metal Substances 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 11
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 239000000376 reactant Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 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
- 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 description 2
- 239000000463 material Substances 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
- 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011160 research Methods 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
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Catalysts (AREA)
- Indole Compounds (AREA)
Abstract
本发明涉及一种用于制备咔唑的催化剂及制备方法。本发明的催化剂的组分由碱金属的无机盐、五氧化二磷、过渡金属氧化物组成。更为具体是本发明的用于制备咔唑的催化剂中各元素组分及含量质量比为V∶Fe∶Ni∶Bi∶K∶P∶Al2O3？=1-10%∶0.2-3%∶0.3-3%∶0.2-2%∶0.2-1%∶0.3-1.5%：80-95%。本发明的该催化剂不使用贵金属，经试验表明，本发明的催化剂还具有催化效率高、生产成本低、应用范围广、经济效益好、节能显著、使用方便等特点。The invention relates to a catalyst for preparing carbazole and a preparation method. The components of the catalyst of the present invention are composed of inorganic salts of alkali metals, phosphorus pentoxide and transition metal oxides. More specifically, is the mass ratio of each element component and content in the catalyst for preparing carbazole of the present invention V:Fe:Ni:Bi:K:P:Al 2 O 3 ? =1-10%: 0.2-3%: 0.3-3%: 0.2-2%: 0.2-1%: 0.3-1.5%: 80-95%. The catalyst of the invention does not use precious metals, and tests show that the catalyst of the invention also has the characteristics of high catalytic efficiency, low production cost, wide application range, good economic benefits, remarkable energy saving, convenient use and the like.
Description
技术领域 technical field
本发明涉及一种用于制备咔唑的催化剂及制备方法。 The invention relates to a catalyst for preparing carbazole and a preparation method.
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。 At present, carbazole is extracted industrially from coal tar. The method of domestic production of carbazole is to use crude anthracene as 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.
中国发明专利申请CN101993411A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 CN101993411A 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 material is easy to get, 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 treatment 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。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. 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 precious metal elements, and there are disadvantages that precious metals are difficult to separate and recover.
发明内容 Contents of the invention
本发明提供一种可克服现有技术不足的、用于制备咔唑且不使用贵金属的催化剂及其制备方法。 The invention provides a catalyst for preparing carbazole without using precious metals and a preparation method thereof, which can overcome the deficiencies of the prior art.
本发明的一种用于制备咔唑的催化剂的组分由碱金属的无机盐、五氧化二磷、过渡金属氧化物组成。 The components of the catalyst used for preparing carbazole in the present invention are composed of alkali metal inorganic salt, phosphorus pentoxide and transition metal oxide.
本发明的用于制备咔唑的催化剂组分中的过渡金属为优选为钒、铁、钼、铬、镍、钴、钨中的任一种或任几种的组合，碱金属为钾。更为具体是本发明的用于制备咔唑的催化剂中各元素组分及含量质量比为V∶Fe∶Ni∶Bi∶K∶P∶Al2O3=1-10%∶0.2-3%∶0.3-3%∶0.2-2%∶0.2-1%∶0.3-1.5%：80-95%。试验表明在该配比下，经过焙烧，V、Fe、Ni、Bi、P的高价态氧化物在二苯胺催化合成咔唑研究中效果最好。碱金属无机盐在以K的无机盐作为助催化剂为最好。 The transition metal in the catalyst component for preparing carbazole of the present invention is preferably any one or combination of any of vanadium, iron, molybdenum, chromium, nickel, cobalt, and tungsten, and the alkali metal is potassium. More specifically, the mass ratio of each element component and content in the catalyst for preparing carbazole of the present invention is V: Fe: Ni: Bi: K: P: Al 2 O 3 =1-10%: 0.2-3% : 0.3-3% : 0.2-2% : 0.2-1% : 0.3-1.5% : 80-95%. Experiments show that under this ratio, after roasting, the high-valence oxides of V, Fe, Ni, Bi, and P have the best effect in the research of diphenylamine-catalyzed synthesis of carbazole. The alkali metal inorganic salt is the best with the inorganic salt of K as the cocatalyst.
本发明制备咔唑的催化剂制备方法是按各组分及含量质量比称取V、Fe、Ni、Bi、K的水溶性盐和五氧化二磷、Al2O3，然后将前述各物质加入草酸水溶液中，经充分浸渍后滤出固体并干燥处理，再进行焙烧使过渡金属盐转变为过渡金属氧化物，经筛分得到本发明的催化剂。 The catalyst preparation method for preparing carbazole in the present invention is to weigh the water-soluble salts of V, Fe, Ni, Bi, K, phosphorus pentoxide, Al 2 O 3 according to each component and content mass ratio, and then add the aforementioned materials In the oxalic acid aqueous solution, the solid is filtered out after being fully soaked and dried, and then roasted to transform the transition metal salt into a transition metal oxide, and the catalyst of the present invention is obtained by sieving.
本发明的制备咔唑的催化剂优选的制备方法是称取：3.40g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。 The preferred preparation method of the catalyst for preparing carbazole of the present invention is to weigh: 3.40g vanadium pentoxide, 2g iron nitrate, 3g nickel nitrate, 1.2g phosphorus pentoxide, 2.4g ammonium molybdate, 2.0g bismuth nitrate and 1g Potassium chloride: Add the above-mentioned substances into 100mL of oxalic acid aqueous solution with a mass concentration of 10%, stir and dissolve at 60-90 o C, then add 80-95g of γ-Al 2 O 3 catalyst carrier for impregnation, and sieve out the size About 30 mesh particles. The size of the catalyst of the present invention is about 30 meshes, which is favorable for catalytic reaction in a fixed bed.
本发明的该催化剂不使用贵金属，经试验表明，本发明的催化剂还具有催化效率高、生产成本低、应用范围广、经济效益好、节能显著、使用方便等特点。 The catalyst of the invention does not use precious metals, and tests show that the catalyst of the invention also has the characteristics of high catalytic efficiency, low production cost, wide application range, good economic benefits, remarkable energy saving, convenient use and the like.
具体实施方式 detailed description
本发明以下结合具体实施方式解说： The present invention is explained below in conjunction with specific embodiment:
一、催化剂的制备 1. Preparation of catalyst
称取3.40g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80-95g载体的γ-Al2O3，质量比按吸附后的催化剂各组分含量质量比（V:Fe：Ni：Bi：K：P：Al2O3=1-10%:0.2-3%:0.3-3%:0.2-2%:0.2-1%:0.3-1.5%：80-95%），上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，便制成了本发明所提及的二苯胺气相一步催化制备咔唑反应用催化剂。 Weigh 3.40g vanadium pentoxide, 2g ferric nitrate, 3g nickel nitrate, 1.2g phosphorus pentoxide, 2.4g ammonium molybdate, 2.0g bismuth nitrate and 1g potassium chloride, add to 100mL oxalic acid aqueous solution, Stir and dissolve at o C temperature, and add 80-95g of γ-Al 2 O 3 as a carrier, the mass ratio is according to the content mass ratio of each component of the catalyst after adsorption (V:Fe:Ni:Bi:K:P:Al 2 O 3 =1-10%:0.2-3%:0.3-3%:0.2-2%:0.2-1%:0.3-1.5%:80-95%), the impregnated catalyst is fully Drying, then roasting at 400°C-800°C for 5-20 hours, sieving into particles with a size of about 30 meshes, and then making the catalyst for the reaction of diphenylamine gas-phase one-step catalytic preparation of carbazole mentioned in the present invention.
二、催化剂的评价 2. Catalyst evaluation
利用管径10mm，管长250mm的固定床反应器对催化剂性能进行评价。首先将30目粒度的催化剂颗粒填充如固定床反应器，并加热至530℃。反应物二苯胺经过预热，利用柱塞泵通过高温水蒸气带入固定床反应器，反应物与水比例（体积比）为1.0∶30，将带有反应物的水蒸气预热至160℃，进入固定床反应器进行反应。固定床反应温度为530℃，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，用气相色谱跟踪监测原料转化率及反应物产率，经实际测试，本催化剂应用于制备咔唑时，原料转化率在小试水平上可达到91%以上，选择性在92%以上。 The performance of the catalyst was evaluated in a fixed-bed reactor with a pipe diameter of 10 mm and a pipe length of 250 mm. First, catalyst particles with a particle size of 30 meshes are filled into a fixed-bed reactor, and heated to 530°C. The reactant diphenylamine is preheated and brought into the fixed-bed reactor through high-temperature steam by a plunger pump. The ratio (volume ratio) of the reactant to water is 1.0:30, and the steam with the reactant is preheated to 160°C , into a fixed-bed reactor for reaction. The fixed bed reaction temperature is 530°C. The high temperature steam flowing out of the fixed bed is passed into the cooling water to dissolve the reaction materials in water, and the conversion rate of raw materials and the yield of reactants are tracked and monitored by gas chromatography. After actual testing, this catalyst is used in When preparing carbazole, the conversion rate of raw materials can reach more than 91% at the laboratory level, and the selectivity is more than 92%.
Claims (6)
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| CN116920837B (en) * | 2023-06-13 | 2024-05-03 | 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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| US6696388B2 (en) * | 2000-01-24 | 2004-02-24 | E. I. Du Pont De Nemours And Company | Gel catalysts and process for preparing thereof |
| CN100379493C (en) * | 2006-04-10 | 2008-04-09 | 武汉大学 | Catalyst for synthesizing p-hydroxybenzonitrile and its preparation method and application |
| CN102008971B (en) * | 2010-10-19 | 2012-08-29 | 黑龙江省科学院石油化学研究院 | Preparation method of pyromellitic dianhydride catalyst |
| CN103638956A (en) * | 2013-11-14 | 2014-03-19 | 中国科学院过程工程研究所 | Catalyst for synthesizing methyl acrylate by trioxymethylene or paraformaldehyde and acetic acid and acetic acid aqueous solution, its preparation and its application method |
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