CN104447353A - Method for directly preparing aniline by virtue of reaction between benzene and hydroxylammonium salt - Google Patents
Method for directly preparing aniline by virtue of reaction between benzene and hydroxylammonium salt Download PDFInfo
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- CN104447353A CN104447353A CN201410751845.4A CN201410751845A CN104447353A CN 104447353 A CN104447353 A CN 104447353A CN 201410751845 A CN201410751845 A CN 201410751845A CN 104447353 A CN104447353 A CN 104447353A
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- benzene
- catalyzer
- aniline
- hydroxylammonium salt
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Abstract
The invention discloses a method for directly preparing aniline by virtue of a reaction between benzene and hydroxylammonium salt. The method comprises the following steps: respectively adding acetic acid, water, hydroxylammonium salt, benzene and a catalyst to a normal pressure reactor equipped with a condensate return device, heating to 70-80 DEG C, and reacting for 2-5h while stirring to obtain aniline, wherein the volume ratio of acetic acid to the water to the benzene is 5 to 5 to 1, the mass ratio of the benzene to the catalyst is (5-20) to 1 and the mole ratio of the benzene to the hydroxylammonium salt is 1 to 1; the catalyst is a vanadium dioxide catalyst (VO2/C) loaded on a carbon material; and the active component VO2 in the catalyst accounts for 3-25% in terms of the total mass of the catalyst. The selectivity of the aniline disclosed by the invention can reach 99% and the yield can reach 41%; and the catalyst is simple in preparation process, low in cost, environmental friendly and easy to operate.
Description
Technical field
The present invention relates to a kind of benzene and hydroxylammonium salt reacts the method directly preparing aniline, a kind of Carbon Materials supports specifically vanadium dioxide catalyzer direct catalysis benzene and hydroxylammonium salt under the reaction conditions of gentleness react the method for one-step synthesis aniline.
Background technology
Aniline is a kind of important Organic Chemicals and fine-chemical intermediate, be widely used in the industries such as medicine, dyestuff, rubber, spices, also be the main raw material producing '-diphenylmethane diisocyanate (MDI), along with the increase of MDI demand, also there is larger growth to the demand of aniline.At present, the industrial process of aniline mainly By Catalytic Hydrogenation of Nitrobenzene method and phenol vapor phase ammonia solution.The By Catalytic Hydrogenation of Nitrobenzene method the first step first uses the mixed solution of concentrated nitric acid and the vitriol oil by nitrated for benzene generation oil of mirbane at 90-140 DEG C, after rectifying is reclaimed, generate aniline again through liquid phase or gas-phase catalytic hydrogenation.Not only energy consumption is high for this synthetic method, etching apparatus, and can produce a large amount of acid sludge, NO
xwaste gas and the waste water containing phenol, cause severe contamination to environment.Phenol vapor phase ammonia solution rule is that phenol and ammonia gas react generate aniline under the high temperature of about 400 DEG C.The synthesis of industrial raw material phenol mainly adopts cumene method, namely with benzene and propylene for raw material, through AlCl
3catalyze and synthesize isopropyl benzene, isopropyl benzene generates superoxide through atmospheric oxidation, and superoxide decomposes and finally obtains phenol and acetone under diluted acid exists.Visible, the problem such as industrial process all exists severe reaction conditions, step is many, energy consumption is high, cost is high, atom utilization is low and environmental pollution is serious of these aniline.Therefore, for adapting to the greenization trend of global Chemical Manufacture, urgently develop new simple, eco-friendly aniline synthetic route.In recent years, synthesize aniline by the direct ammoxidation of benzene, polystep reaction is become a step, can Atom economy be significantly improved, and by product is hydrogen or water environmentally safe, is thus subject to the extensive concern of investigator.
Professor Hu Changwei of Sichuan University reports a kind of method being prepared aniline by the direct amination of benzene, the method is using ammoniacal liquor as aminating agent, hydrogen peroxide as oxygenant, Ni, Cu, Ce, V, Ti metal catalyst (patent publication No.: CN101906045) that the catalyzer of use supports for titanium-silicon molecular sieve TS-1.Although this method reaction conditions is gentle, environmental pollution is little, carrier TS-1 is expensive, catalyzer cost is higher, and the Transform Law rate of benzene very low (lower than 10%), aniline yield low.
Zhu Liangfang etc. are with γ-Al
2o
3for carrier, the catalyzer made using two or three in nickel, molybdenum, vanadium, zirconium, manganese, cerium as active ingredient is in a step ammoxidation of benzene (patent publication No.: CN1555921).This patent is also using ammoniacal liquor as aminating agent, and hydrogen peroxide is as oxygenant, although reaction conditions is gentle, the yield of aniline is only 0.038%, and catalyzer needs multistage roasting, preparation process more complicated, needs hydrogen reducing to activate before use.In addition, in order to solve using ammoniacal liquor as the low restriction of aminating agent aniline yield rate, this seminar proposes with solubility vanadic salts (vanadylic sulfate, ammonium meta-vanadate, sodium metavanadate) for catalyzer in patent 200510020505, and oxammonium hydrochloride is as the method for aminating agent one-step synthesis aniline in aqueous acetic acid.This method makes the yield of aniline reach 68%, although the method substantially increases the yield of aniline, soluble vanadium salt catalyst is expensive, can not recycle and reuse, cost is higher, thus also limit the industrial application of the method.
Carbon Materials has higher specific surface area and large pore volume and higher hydrothermal stability and anti acid alkali performance energy due to it, is all widely used at field tools such as fuel cell, sensor, fractionation by adsorption, catalysis.Biomass are that the earth exists material the most widely, be that precursor prepares Carbon Materials not only Cheap highly effective, simple but also environmental sound, therefore become the focus of Recent study with biomass.In addition, up to the present, the application that Carbon Materials supports vanadium dioxide, molybdenum dioxide catalyzer react in the reaction of single stage method aniline at benzene and hydroxylammonium salt is not also reported.
Summary of the invention
A kind of benzene and hydroxylammonium salt is the object of the present invention is to provide to react the method directly preparing aniline, the vanadium dioxide catalyzer that the method uses a kind of Carbon Materials to support, can catalysis benzene and hydroxylammonium salt react a step and obtain aniline and there is very high selectivity and reactive behavior under the reaction conditions of gentleness, simultaneously, this method for preparing catalyst process is simple, easy to operate, with low cost.
The technical solution used in the present invention is:
Benzene and hydroxylammonium salt react a method for directly aniline processed, and the method comprises the steps:
Add acetic acid, water, hydroxylammonium salt, benzene and catalyzer respectively to in the normal pressure reactor of condensation reflux unit, be warming up to 70-80 DEG C, stirring the lower reaction times is 2-5h, obtains aniline;
Wherein, volume ratio is acetic acid: water: benzene=5:5:1, and quality is than benzene: catalyzer=5 ~ 20:1, mol ratio benzene: hydroxylammonium salt=1:1, and described catalyzer is that the vanadium dioxide catalyzer that Carbon Materials supports (is called for short VO
2/ C), active ingredient VO in this catalyzer
2account for 3 ~ 25% of catalyzer total mass.
Described hydroxylammonium salt is oxammonium hydrochloride or oxammonium sulfate.
A preparation method for the vanadium dioxide catalyzer that Carbon Materials supports, comprises the steps
Ammonium meta-vanadate and sucrose are joined in deionized water, solution is poured into water heating kettle after dissolving, in 80-180 DEG C of thermal treatment 6-48 hour after airtight, to washing lotion neutrality, drying, obtain brown solid finally by filtration, hot wash, this solid in a nitrogen atmosphere 500-900 DEG C of charing 3-8 hour final black charcoal that obtains carries vanadium dioxide catalyzer (VO
2/ C);
Wherein, material proportion is mol ratio ammonium meta-vanadate: sucrose=1:1 ~ 15, adds 1.3 ~ 19.9mmol ammonium meta-vanadate in every 60 ml deionized water.
Effect of the present invention and benefit are: the reaction that catalyzer of the present invention reacts single stage method aniline for benzene and hydroxylammonium salt has very high selectivity and reactive behavior, the selectivity of aniline can reach 99%, yield can reach 41%, compared with the good soluble vanadium salt catalyst of the catalytic performance of bibliographical information, solid catalyst provided by the invention is easy to and being separated of product after the completion of reaction, and catalyzer is reusable after centrifugation, there is good application prospect.Compared with the traditional preparation methods pickling process of loaded catalyst, the preparation method of catalyzer involved in the present invention adopts the method for Hydrothermal Synthesis, aqueous sucrose solution is mixed the precursor simultaneously obtaining carrier and active ingredient through a step hydrothermal treatment consists with metal precursor, the content of catalyst activity component can be regulated by the concentration of modulation metal precursor, and the preparation of catalyzer is using abundant biomass resource sucrose as the precursor of high-area carbon, do not need additionally to use other catalyzer to carry out the hydrolytie polycondensation of catalysing sucrose, with low cost, environmental friendliness and preparation process is simple, easy to operate, there are good application and industrialization prospect.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the embodiment of the present invention 1 Kaolinite Preparation of Catalyst.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
VO
2the preparation of/C-1# catalyzer: by 1.0g (8.5mmol) ammonium meta-vanadate and 6.8g (19.9mmol) sucrose dissolved in 60mL deionized water, pour solution into water heating kettle until completely dissolved, in 120 DEG C of thermal treatments 12 hours after airtight, after being down to room temperature, to washing lotion neutrality, drying, obtain brown catalyst precursor through filtration, hot wash.By this catalyst precursor 550 DEG C of charings, 6 hours final black solids in a nitrogen atmosphere, from the XRD spectra of Fig. 1, except the steamed bun peak of unformed charcoal, other characteristic diffraction peaks and standard substance VO
2(PDF 01-073-2362) coincide, and therefore gained catalyst activity component is VO
2.Seteram Setsys 16/18 thermal analyzer carries out thermogravimetric (TG) analysis to catalyzer, as calculated VO in known prepared catalyzer
2account for 15% of catalyzer total mass.
Embodiment 2
VO
2the preparation of/C-2# catalyzer: preparation process is identical with embodiment 1, difference is that the amount of added ammonium meta-vanadate is 0.39g (3.3mmol), obtains VO in catalyzer through thermogravimetric (TG) analytical calculation
2account for 4% of catalyzer total mass.
Embodiment 3
VO
2the preparation of/C-3# catalyzer: preparation process is identical with embodiment 1, difference is that the amount of added ammonium meta-vanadate is 0.60g (5.1mmol), obtains VO in catalyzer through thermogravimetric (TG) analytical calculation
2account for 6% of catalyzer total mass.
Embodiment 4
VO
2the preparation of/C-4# catalyzer: preparation process is identical with embodiment 1, difference is that the amount of added ammonium meta-vanadate is 2.0g (17.1mmol), obtains VO in catalyzer through thermogravimetric (TG) analytical calculation
2account for 20% of catalyzer total mass.
Embodiment 5
Benzene and oxammonium hydrochloride react the reaction of directly aniline processed: to be equipped with stir and condensation reflux unit 100mL there-necked flask in add 5mL acetic acid and 5mL water, add 0.78g (11.25mmol) oxammonium hydrochloride subsequently, be stirred at 30 DEG C and dissolve completely, add 0.1g VO successively
2/ C-1# catalyzer and 1mL (11.25mmol, 0.89g) benzene, be warming up to 80 DEG C of reactions 4 hours afterwards.After reaction terminates, be down to room temperature, use the NaOH solution neutralization reaction liquid of 30wt% to its PH=7 ~ 8 after catalyzer centrifugation, go out organic phase by 5mL extracted with diethyl ether, carry out qualitative analysis by gas-chromatography, carry out quantitative analysis with area normalization method.
Embodiment 6
Concrete reaction process is identical with embodiment 5, and difference is that used catalyst is VO
2/ C-2# catalyzer.
Embodiment 7
Concrete reaction process is identical with embodiment 5, and difference is that used catalyst is VO
2/ C-3# catalyzer.
Embodiment 8
Concrete reaction process is identical with embodiment 5, and difference is that used catalyst is VO
2/ C-4# catalyzer.
Embodiment 9
VO
2the reusability of/C-1# catalyzer: reaction process is identical with embodiment 5, difference is that used catalyst is the VO that embodiment 5 reacts rear recovery
2/ C-1# catalyzer.
Embodiment 10
Benzene reacts the reaction of directly aniline processed with oxammonium sulfate: concrete reaction process is identical with embodiment 5 with material proportion, and difference is that hydroxylammonium salt used is oxammonium sulfate.
Table 1 is the reaction result of embodiment of the present invention 5-10.
Unaccomplished matter of the present invention is known technology.
Claims (3)
1. benzene and hydroxylammonium salt react a method for directly aniline processed, it is characterized by the method and comprise the steps:
Add acetic acid, water, hydroxylammonium salt, benzene and catalyzer respectively to in the normal pressure reactor of condensation reflux unit, be warming up to 70-80 DEG C, stirring the lower reaction times is 2-5h, obtains aniline;
Wherein, volume ratio is acetic acid: water: benzene=5:5:1, and quality is than benzene: catalyzer=5 ~ 20:1, mol ratio benzene: hydroxylammonium salt=1:1, and described catalyzer is that the vanadium dioxide catalyzer that Carbon Materials supports (is called for short VO
2/ C), active ingredient VO in this catalyzer
2account for 3 ~ 25% of catalyzer total mass.
2. benzene as claimed in claim 1 and hydroxylammonium salt react the method for directly aniline processed, and it is characterized by described hydroxylammonium salt is oxammonium hydrochloride or oxammonium sulfate.
3. the preparation method of vanadium dioxide catalyzer that supports of Carbon Materials, comprises the steps
Ammonium meta-vanadate and sucrose are joined in deionized water, solution is poured into water heating kettle after dissolving, in 80-180 DEG C of thermal treatment 6-48 hour after airtight, to washing lotion neutrality, drying, obtain brown solid finally by filtration, hot wash, this solid in a nitrogen atmosphere 500-900 DEG C of charing 3-8 hour final black charcoal that obtains carries vanadium dioxide catalyzer (VO
2/ C);
Wherein, material proportion is mol ratio ammonium meta-vanadate: sucrose=1:1 ~ 15, adds 1.3 ~ 19.9mmol ammonium meta-vanadate in every 60 ml deionized water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829463A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Environment-friendly synthesis method of 1-naphthylamine |
| CN104829462A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Method for synthesizing 1,5-diaminonaphthalene by one step with naphthalene |
| CN105523907A (en) * | 2015-12-14 | 2016-04-27 | 河北工业大学 | Method for directly preparing cyclohexanone from benzene |
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| US2585355A (en) * | 1952-02-12 | Method of introducing an amino | ||
| US3832364A (en) * | 1972-05-25 | 1974-08-27 | Du Pont | Amination of aromatic compounds in liquid hydrogen fluoride |
| CN1706807A (en) * | 2004-06-09 | 2005-12-14 | 四川大学 | Direct one-step amination process of synthesizing toluidine from toluene |
| CN1807397A (en) * | 2005-03-14 | 2006-07-26 | 四川大学 | One-step method for synthesizing phenylamine from direct oxidation and amination of bezene |
| CN103554997A (en) * | 2013-10-16 | 2014-02-05 | 张家港环纳环保科技有限公司 | Carbon-coated vanadium dioxide nanoparticles and preparation method thereof |
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2014
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2585355A (en) * | 1952-02-12 | Method of introducing an amino | ||
| US3832364A (en) * | 1972-05-25 | 1974-08-27 | Du Pont | Amination of aromatic compounds in liquid hydrogen fluoride |
| CN1706807A (en) * | 2004-06-09 | 2005-12-14 | 四川大学 | Direct one-step amination process of synthesizing toluidine from toluene |
| CN1807397A (en) * | 2005-03-14 | 2006-07-26 | 四川大学 | One-step method for synthesizing phenylamine from direct oxidation and amination of bezene |
| CN103554997A (en) * | 2013-10-16 | 2014-02-05 | 张家港环纳环保科技有限公司 | Carbon-coated vanadium dioxide nanoparticles and preparation method thereof |
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|---|
| YU FEN LU等: "Direct amination of benzene to aniline with several typical vanadium complexes", 《CHINESE CHEMICAL LETTERS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104829463A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Environment-friendly synthesis method of 1-naphthylamine |
| CN104829462A (en) * | 2015-05-20 | 2015-08-12 | 湘潭大学 | Method for synthesizing 1,5-diaminonaphthalene by one step with naphthalene |
| CN105523907A (en) * | 2015-12-14 | 2016-04-27 | 河北工业大学 | Method for directly preparing cyclohexanone from benzene |
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