CN101906045A - Method for directly synthesizing aniline from benzene and ammonia by one step - Google Patents
Method for directly synthesizing aniline from benzene and ammonia by one step Download PDFInfo
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- CN101906045A CN101906045A CN2010102185663A CN201010218566A CN101906045A CN 101906045 A CN101906045 A CN 101906045A CN 2010102185663 A CN2010102185663 A CN 2010102185663A CN 201010218566 A CN201010218566 A CN 201010218566A CN 101906045 A CN101906045 A CN 101906045A
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Abstract
The invention discloses a method for directly synthesizing aniline from benzene and ammonia by one step, which takes benzene as a raw material, ammonia as an aminating agent, hydrogen peroxide as an oxidizer, acetonitrile as a solvent and TS-1 loaded by metal as a catalyst. The method for synthesizing aniline by one step has the characteristics of high yield of aniline, mild reaction condition, simple catalyst preparing process and easily obtained cheap raw materials, thus being a green synthesis method which has low cost and high yield and is simple and practicable.
Description
Technical field
The present invention relates to a kind of method of directly synthesizing aniline by benzene and ammoniacal liquor.
Background technology
Aniline is important Organic Chemicals and fine-chemical intermediate, is widely used in urethane, rubber ingredients, dyestuff, pigment, agricultural chemicals, medicine, and industrial circle such as special fibre.
Existing Aniline Production route is that oil of mirbane is carried out reduction under shortening or other conditions, or with phenol, halogeno-benzene and amino displacement and obtain.These methods exist shortcomings such as operational condition harshness (High Temperature High Pressure), Atom economy difference, cause environmental hazard to a certain extent, therefore do not meet the needs of sustainable Green Chemistry industrial development and low-carbon economy.Adopt novel method directly amino to be introduced phenyl ring, realize obviously improving the atom utilization of reaction, important meaning is arranged economizing on resources and eliminating environmental pollution by the synthetic aniline of benzene single step reaction.
Thomas etc. at first proposed in Canadian Patent No.553988 by benzene and ammonia under a kind of reducible metal (as Fe, Ni, Co, Sn etc.) oxide compound effect in 1958, gas-phase reaction one-step synthesis aniline in 100-1000 ℃ of temperature range.Afterwards at US-A-2948755, JP-A06/293715, US Patent Nos.3919155 and 3929889 has mentioned similar process among the US Patent No.4031106.These methods all be with ammonia or anhydrous ammonia as ammoniation agent, catalyzer has been used VI-B family, VIII family metal element compound and a kind of easy reductive metal oxide.Yet the shortcoming that these processes still exist severe reaction conditions (High Temperature High Pressure), transformation efficiency or selectivity not to get both.As: benzene is at Fe-SiO
2Under the catalyst action, generate aniline in 400 ℃ of aminations, wherein the transformation efficiency of benzene is 0.85%, and the selectivity of aniline is 97.3%.
Zhu Liangfang etc. have proposed with solubility vanadic salts (vanadylic sulfate, ammonium meta-vanadate, sodium metavanadate) as catalyzer in patent ZL 2,005 1 0020505.5 and journal of Catalysis 245 (2007) 446-455, use the method for oxammonium hydrochloride as ammoniation agent one-step synthesis aniline in acetate solvate, this method aniline molar yield can reach 68%, and selectivity is also more than 90%.Lv Yufen etc. in Chinese Chemical Letters 2009 (20) 238-240, reported adopt vanadium complex compound as catalyzer, acetic acid is as solvent, oxammonium hydrochloride as ammoniation agent by benzene one-step synthesis aniline.The molar yield 42% of aniline, selectivity can reach near 100%.People such as K.M.Prada propose to adopt the adulterated MCM-41 of Mn (Mn-MCM-41) as catalyzer in Applied Catalysis A:General 2008 (351) 59-67, azanol is as ammoniation agent, synthetic aniline in acetate solvate, the aniline molar yield reaches 68.5%, selectivity 100%.Although all obtained than higher yield and selectivity as ammoniation agent by azanol, because the costing an arm and a leg of azanol itself, explosive and have toxicity, all there are certain risk in production and preservation process, and the industrial application of this method is restricted.
Based on the needs of Green Chemistry and Sustainable development, under mild conditions, by cheap ammoniacal liquor as ammoniation agent, H
2O
2As oxygenant and benzene one-step synthesis aniline, be one and have the research direction that challenge reached and obtained concern.Zhu Liangfang etc. have proposed with Al in patent ZL 2,004 1 0021636.0
2O
3As carrier, with two or three method for preparing catalyst in nickel, molybdenum, vanadium, manganese, zirconium, the cerium as active constituent, this catalyst series is applied to a step ammoxidation of benzene, reaction conditions be normal pressure, 50 ℃ the reaction two hours, the molar yield of high aniline is 0.038%, and corresponding selectivity is 86%.This process condition gentleness, the raw material cheapness, but yield is not ideal enough, and the catalyst preparation process complexity, the reaction procatalyst need carry out hydrogen reducing.Zhu Liangfang etc. are at Industrial; Among Engineering Chemistry Research 46 (2007) 3443-3445, adopted the method for catalytic distillation that process intensification is carried out in above-mentioned reaction, obtaining under normal pressure, 80 ℃ of conditions, the molar yield of high aniline is 0.13%.This method makes aniline yield rate than still reaction raising arranged.
Summary of the invention
The objective of the invention is to adopt cheap ammoniacal liquor as ammoniation agent, hydrogen peroxide provides a kind of working method simple as oxygenant, the reaction conditions gentleness, high reactivity and highly selective be the method for raw material one-step synthesis aniline with benzene.
The present invention is raw material with benzene, ammoniacal liquor is as ammoniation agent, hydrogen peroxide is as oxygenant, it is characterized in that adopting Ni, Cu, Ce, V, a kind of among the Ti as active ingredient, TS-1 is as the metal load type catalyst of carrier, wherein the content of metal mass percent is 2.5-10%, as solvent is water, acetonitrile, the trimethyl carbinol, N,N-DIMETHYLACETAMIDE, a kind of among the DMSO, by quality than benzene: catalyzer=44: 1-4, volume ratio benzene: ammoniacal liquor: hydrogen peroxide: solvent=1: 1-5: 1-5: 1-5, at normal pressure, under the 40-80 ℃ of condition, stirred 2-6 hour, the hydrogen peroxide discontinuity joining day was spaced apart 12 minutes/time-60 minutes/time, filtered after chromatographic separation gets product aniline.
Metal load Preparation of Catalyst schedule of operation: will place an oral examination pipe with the HTS (TS-1) of hydrothermal synthesis method preparation, be 0.9 * 10 25 ℃ of suctions
2KPa; A cut-out oral examination pipe is connected with vacuum pump, keeps vacuum state in vitro, adopts the solution impregnating carrier of single nickel salt, copper sulfate, sodium metavanadate, titanous chloride, cerous nitrate respectively, still aging 24 hours; To prop up the oral examination pipe and move into loft drier, and be evacuated to drying at 25 ℃, vacuum tightness is 0.9 * 10
2KPa; To flood and dried catalyzer immigration crucible, 500 ℃ of roastings 4 hours.The roasting rear catalyst is preserved standby in exsiccator.
As catalyzer best be the TS-1 catalyzer (Ni/TS-1, Cu/TS-1, V/TS-1) of nickel, copper, vanadium load, optimum metal component load quality per-cent is 2.5-7.5%, also can directly use carrier TS-1 as catalyzer.Best solvent is acetonitrile, the trimethyl carbinol, N,N-DIMETHYLACETAMIDE.The mass ratio of optimum benzene and catalyzer is a benzene: catalyzer=44: 2-4, optimum volume ratio benzene: ammoniacal liquor: hydrogen peroxide: solvent=1: 2-5: 2-4: the 2-4 wherein mass percent concentration of ammoniacal liquor and hydrogen peroxide is respectively 25% and 30%.Optimum temperature of reaction 60-80 ℃, the optimum reaction times is 2-4 hour.
The present invention with the TS-1 of metal component load as catalyzer, with neutral solvent as reaction medium, with ammoniacal liquor as ammoniation agent, hydrogen peroxide directly prepares aniline as oxygenant method except have reaction raw materials cheap, be easy to get process safety; Product is easy to separate; Generate advantages such as water, environmental sound behind the hydroperoxidation, also have following outstanding characteristics:
(1) catalytic reaction condition gentleness just can be carried out under normal pressure and lesser temps;
(2) aniline yield rate height the highlyest can reach 7.9%, and corresponding aniline selectivity can reach 87.7%;
(3) method for preparing catalyst is simple;
(4) the catalyzed reaction time is short;
(5) unreacted ammoniacal liquor and benzene and solvent all can reclaim once more and utilize.
Therefore, the present invention has the application prospect of research and development.
Embodiment
Embodiment 1 takes by weighing 0.1143g NiSO respectively
4, 0.1007g CuSO
45H
2O, 0.0795g CeN
5O
96H
2O, 0.1004g VOSO
4NH
2O, 0.5127g TiCl
3NH
2O (35%) is in the 2mL deionized water, and heated and stirred is to all dissolvings, and is standby.Take by weighing 5 parts of 1g TS-1 powders and place 5 oral examination pipes respectively, vacuumized 0.5 hour at 25 ℃, vacuum tightness is 0.9 * 10
2KPa, when keeping vacuum tightness, 5 parts of metal salt solutions that will prepare are respectively poured in 5 mouthful invisible spectro carriers while hot, still aging 24 hours; To prop up the oral examination pipe and move into loft drier, under 120 ℃ of temperature, dry, dried catalyzer be moved into crucible, 500 ℃ of following roastings 4 hours to complete drying.Catalyzer is labeled as Ni/TS-1, Cu/TS-1, Ce/TS-1, V/TS-1, Ti/TS-1, more than 5 kinds of catalyst metal load quality per-cents to be 2.5%, kept dry is standby.
Embodiment 2 takes by weighing 0.2286g, 0.3429g, 0.4572gNiSO respectively
4According to the method for embodiment 1, preparation Ni/TS-1 catalyzer, wherein the nickel loading mass percent is respectively 5.0%, 7.5%, 10.0%.
Embodiment 3 takes by weighing TS-1, Ni/TS-1, V/TS-1, Cu/TS-1, Ce/TS-1, Ti/TS-1 (wherein the metal load mass percent is 2.5%) 0.3g respectively in the two neck bottles of 6 50mL, each adds 5mL benzene and 10mL 25% ammoniacal liquor, be stirred and heated to 70 ℃, add 2mL30%H
2O
2, added 2mL 30%H afterwards every 24 minutes
2O
2, add 10mL 30%H altogether
2O
2, the reaction times is 2 hours, the catalyzer that obtains the different metal load optionally influences aniline yield rate and aniline, the results are shown in Table one.
The catalyzer of table one different metal load is to aniline yield rate and optionally influence
Embodiment 4 take by weighing respectively the Ni mass percent be 2.5%, 5.0%, 7.5%, 10.0% Ni/TS-1 catalyzer 0.3g in the two neck bottles of 4 50mL, each adds 5mL benzene and 10mL25% ammoniacal liquor, is stirred and heated to 70 ℃, adds 2mL 30%H
2O
2, added 2mL 30%H afterwards every 24 minutes
2O
2, add 10mL 30%H altogether
2O
2, the reaction times is 2 hours, the catalyzer that obtains different nickel loadings optionally influences aniline yield rate and aniline.The results are shown in Table two
The catalyzer of the different nickel loadings of table two optionally influences aniline yield rate and aniline
Embodiment 5 takes by weighing 5 parts of Ni/TS-1 (the Ni mass percent is 2.5%) 0.3g respectively and places 5 50mL, two neck bottles, all add 5mL benzene, 10mL25% ammoniacal liquor, and add 15mL water, acetonitrile, methyl-sulphoxide, the trimethyl carbinol, N respectively, the N-N,N-DIMETHYLACETAMIDE, be stirred and heated to 70 ℃, add 2mL 30%H
2O
2, added 2mL 30%H afterwards every 24 minutes
2O
2, add 10mL 30%H altogether
2O
2, the reaction times is 2 hours, obtaining different solvents optionally influences aniline yield rate and aniline, the results are shown in Table three.
Table three different solvents optionally influences aniline yield rate and aniline
Embodiment 6 takes by weighing 5 parts of Ni/TS-1 (the Ni mass percent is 2.5%) 0.3g respectively and places 5 50mL, two neck bottles, all add 5mL benzene, 10mL25% ammoniacal liquor, and add 5,10,15,20 respectively, the 25mL acetonitrile, be stirred and heated to 70 ℃, add 2mL 30%H
2O
2, added 2mL 30%H afterwards every 24 minutes
2O
2, add 10mL 30%H altogether
2O
2, the reaction times is 2 hours, obtaining different acetonitrile consumptions optionally influences aniline yield rate and aniline, the results are shown in Table four.
The different acetonitrile consumptions of table four optionally influence aniline yield rate and aniline
Embodiment 7 takes by weighing 3 parts of Ni/TS-1 (the Ni mass percent is 2.5%) 0.3g and places 3 50mL, two neck bottles, all adds 5mL benzene, 10mL25% ammoniacal liquor and 15mL acetonitrile, is stirred and heated to 70 ℃.Add H at interval with three kinds of different times respectively
2O
2And maintenance adding total amount is 10mL.Concrete operations are the initial adding 5mL 30%H of (1) reaction
2O
2, added 5mL 30%H afterwards again every 60 minutes
2O
2(2) the initial adding 2mL 30%H of reaction
2O
2, added 2mL 30%H afterwards every 24 minutes
2O
2(3) the initial adding 1mL30%H of reaction
2O
2, added 1mL 30%H afterwards every 12 minutes
2O
2, the reaction times is 2 hours, obtains H
2O
2Joining day optionally influences for the yield and the aniline of aniline at interval, the results are shown in table five.
Table five H
2O
2Joining day optionally influences for the yield and the aniline of aniline at interval
Embodiment 8 takes by weighing Ni/TS-1 (the Ni mass percent is 2.5%) 0.1g, 0.2g, 0.3g, 0.4g respectively, 0.5g places 5 50mL, two neck bottles, all add 5mL benzene, 10mL25% ammoniacal liquor and 15mL acetonitrile, be stirred and heated to 70 ℃, add 2mL 30%H
2O
2, added 2mL30%H afterwards every 24 minutes
2O
2, add 10mL 30%H altogether
2O
2, the reaction times is 2 hours, obtaining catalyst levels optionally influences for aniline yield rate and aniline, the results are shown in table six.
Table six different catalysts consumption optionally influences aniline yield rate and aniline
Embodiment 9 takes by weighing 5 parts of Ni/TS-1 (the Ni mass percent is 2.5%) 0.3g respectively and places 5 50mL, two neck bottles, adds 5mL benzene, 10mL25% ammoniacal liquor and 15mL acetonitrile, is stirred and heated to 70 ℃.Regulate H
2O
2Add total amount, be respectively 5,10,15,20,25mL, concrete operation method be that (1) reacts initial adding 1mL30%H
2O
2, added 1mL30%H afterwards every 24 minutes
2O
2(2) the initial adding 2mL30%H of reaction
2O
2, added 2mL30%H afterwards every 24 minutes
2O
2(3) the initial adding 3mL30%H of reaction
2O
2, added 3mL30%H afterwards every 24 minutes
2O
2(4) the initial adding 4mL30%H of reaction
2O
2, added 4mL30%H afterwards every 24 minutes
2O
2(5) the initial adding 5mL30%H of reaction
2O
2, added 5mL30%H afterwards every 24 minutes
2O
2, the reaction times is 2 hours, obtains H
2O
2Add-on the results are shown in Table seven for aniline yield rate and optionally influence.
The different H of table seven
2O
2Add-on optionally influences aniline yield rate and aniline
Embodiment 10 takes by weighing 5 parts of Ni/TS-1 (the Ni mass percent is 2.5%) 0.3g respectively and places 5 50mL, two neck bottles, all add 5mL benzene, 15mL acetonitrile, add 5,10,15,20 respectively, 25mL25% ammoniacal liquor, be stirred and heated to 70 ℃, add 2mL 30%H
2O
2, added 2mL30%H afterwards every 24 minutes
2O
2, add 10mL H altogether
2O
2, the reaction times is 2 hours, obtaining different ammonia volume optionally influences aniline yield rate and aniline, the results are shown in table eight.
The different ammonia volume of table eight optionally influence aniline yield rate and aniline
Embodiment 11 takes by weighing 5 parts of Ni/TS-1 (the Ni mass percent is 2.5%) 0.3g respectively and places 5 50mL, two neck bottles, adds 5mL benzene, 10mL25% ammoniacal liquor and 15mL acetonitrile, is stirred and heated to 40,50,60,70,80 ℃ respectively, adds 2mL 30%H
2O
2, added 2mL 30%H afterwards every 24 minutes
2O
2, add 10mL H altogether
2O
2, the reaction times is 2 hours, obtaining temperature of reaction optionally influences for aniline yield rate and aniline, the results are shown in table nine.
Table nine differential responses temperature optionally influences aniline yield rate and aniline
Embodiment 12 takes by weighing Ni/TS-1 (the Ni mass percent is 2.5%) 0.3g and places 50mL two neck bottles, adds 5mL benzene, 10mL25% ammoniacal liquor and 15mL acetonitrile, is stirred and heated to 70 ℃, adds 2mL30%H
2O
2, added 2mL30%H afterwards every 24 minutes
2O
2, stop to add H after two hours
2O
2Continue reaction 2 hours, reacted altogether 4 hours, obtain aniline yield rate 5.1%, aniline selectivity 77.9%.
Embodiment 13 takes by weighing Ni/TS-1 (the Ni mass percent is 2.5%) 0.3g and places 50mL two neck bottles, adds 5mL benzene, 10mL25% ammoniacal liquor and 15mL acetonitrile, is stirred and heated to 80 ℃, adds 2mL30%H
2O
2, added 2mL30%H afterwards every 24 minutes
2O
2, stop to add H after two hours
2O
2Continue reaction 4 hours, reacted altogether 6 hours, obtain aniline yield rate 5.0%, aniline selectivity 73.2%.
Claims (9)
1. method for preparing aniline by benzene one direct one-step amination, with benzene is raw material, ammoniacal liquor is as ammoniation agent, hydrogen peroxide is as oxygenant, it is characterized in that adopting Ni, Cu, Ce, V, a kind of among the Ti as active ingredient, TS-1 is as the metal load type catalyst of carrier, wherein the content of metal mass percent is 2.5-10%, as solvent is water, acetonitrile, the trimethyl carbinol, N,N-DIMETHYLACETAMIDE, a kind of among the DMSO, by quality than benzene: catalyzer=44: 1-4, volume ratio benzene: ammoniacal liquor: hydrogen peroxide: solvent=1: 1-5: 1-5: 1-5, at normal pressure, under the 40-80 ℃ of condition, stirred 2-6 hour, the hydrogen peroxide discontinuity joining day was spaced apart 12 minutes/time-60 minutes/time, filtered after chromatographic separation gets product aniline.
2. by the described method of claim 1, it is characterized in that metal load type catalyst adopts Ni as active ingredient.
3. by the described method of claim 1, it is characterized in that the metal load mass percent is 2.5-7.5% in the catalyzer.
4. by the described method of claim 1, it is characterized in that quality is than benzene: catalyzer=44: 2-4.
5. by the described method of claim 1, it is characterized in that solvent is an acetonitrile.
6. by the described method of claim 1, it is characterized in that volume ratio benzene: ammoniacal liquor: hydrogen peroxide: solvent=1: 2-5: 2-4: 2-4.
7. by the described method of claim 1, it is characterized in that reaction times 2-4 hour.
8. by the described method of claim 1, it is characterized in that temperature of reaction 60-80 ℃.
9. by the described method of claim 1, it is characterized in that the hydrogen peroxide joining day was spaced apart 24 minutes/time-60 minutes/time.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103408434A (en) * | 2013-08-16 | 2013-11-27 | 四川大学 | Method for synthesizing aniline by directly oxidizing and aminating benzene by one step |
CN103420851A (en) * | 2013-08-23 | 2013-12-04 | 湘潭大学 | Method for preparing 1,5-diaminonaphthalene through naphthalene in one step and application of catalysts |
CN106699571A (en) * | 2016-11-16 | 2017-05-24 | 南京工业大学 | Preparation method of 2,5-dichloroaniline |
CN112209835A (en) * | 2020-09-18 | 2021-01-12 | 江苏方圆芳纶研究院有限公司 | Method for preparing p-phenylenediamine |
EP4345085A1 (en) | 2022-09-28 | 2024-04-03 | The Goodyear Tire & Rubber Company | Rubber additive from biomass through syngas production |
EP4345125A1 (en) | 2022-09-28 | 2024-04-03 | The Goodyear Tire & Rubber Company | Rubber additive from end of life tires through syngas production |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1706808A (en) * | 2004-06-09 | 2005-12-14 | 四川大学 | Direct one-step aminating synthesis of toluidine from toluene |
-
2010
- 2010-07-06 CN CN 201010218566 patent/CN101906045B/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1706808A (en) * | 2004-06-09 | 2005-12-14 | 四川大学 | Direct one-step aminating synthesis of toluidine from toluene |
Non-Patent Citations (3)
Title |
---|
CHANGWEI HU ET.AL.: "Direct Amination of Benzene to Aniline by Aqueous Ammonia and Hydrogen Peroxide over V-Ni/Al2O3 Catalyst with Catalytic Distillation", 《IND. ENG. CHEM. RES.》 * |
夏云生 等: "镍-钒催化剂作用下由苯直接氧化氨化合成苯胺", 《物理化学学报》 * |
祝良芳: "由苯直接催化氧化氨基化一步合成苯胺的研究", 《中国博士学位论文全文数据库(工程科技I辑)》 * |
Cited By (8)
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CN103408434A (en) * | 2013-08-16 | 2013-11-27 | 四川大学 | Method for synthesizing aniline by directly oxidizing and aminating benzene by one step |
CN103408434B (en) * | 2013-08-16 | 2014-11-26 | 四川大学 | Method for synthesizing aniline by directly oxidizing and aminating benzene by one step |
CN103420851A (en) * | 2013-08-23 | 2013-12-04 | 湘潭大学 | Method for preparing 1,5-diaminonaphthalene through naphthalene in one step and application of catalysts |
CN106699571A (en) * | 2016-11-16 | 2017-05-24 | 南京工业大学 | Preparation method of 2,5-dichloroaniline |
CN112209835A (en) * | 2020-09-18 | 2021-01-12 | 江苏方圆芳纶研究院有限公司 | Method for preparing p-phenylenediamine |
CN112209835B (en) * | 2020-09-18 | 2023-10-27 | 江苏方圆芳纶研究院有限公司 | Method for preparing p-phenylenediamine |
EP4345085A1 (en) | 2022-09-28 | 2024-04-03 | The Goodyear Tire & Rubber Company | Rubber additive from biomass through syngas production |
EP4345125A1 (en) | 2022-09-28 | 2024-04-03 | The Goodyear Tire & Rubber Company | Rubber additive from end of life tires through syngas production |
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