CN104402736B - Benzene and the hydroxylammonium salt of the catalysis of a kind of loading type molybdenum dioxide react the method directly preparing aniline - Google Patents
Benzene and the hydroxylammonium salt of the catalysis of a kind of loading type molybdenum dioxide react the method directly preparing aniline Download PDFInfo
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- CN104402736B CN104402736B CN201410751457.6A CN201410751457A CN104402736B CN 104402736 B CN104402736 B CN 104402736B CN 201410751457 A CN201410751457 A CN 201410751457A CN 104402736 B CN104402736 B CN 104402736B
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- hydroxylammonium salt
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 96
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 64
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 27
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 8
- 238000011068 loading method Methods 0.000 title claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 7
- 239000004480 active ingredient Substances 0.000 claims abstract description 6
- 238000009833 condensation Methods 0.000 claims abstract description 4
- 230000005494 condensation Effects 0.000 claims abstract description 4
- -1 hydroxylammonium salt Chemical class 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000010792 warming Methods 0.000 claims abstract description 4
- 230000035484 reaction time Effects 0.000 claims abstract description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 229930006000 Sucrose Natural products 0.000 claims description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical group Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- VGYYSIDKAKXZEE-UHFFFAOYSA-L hydroxylammonium sulfate Chemical compound O[NH3+].O[NH3+].[O-]S([O-])(=O)=O VGYYSIDKAKXZEE-UHFFFAOYSA-L 0.000 claims description 4
- 239000003610 charcoal Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 description 17
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 150000003681 vanadium Chemical class 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention is that the benzene of a kind of loading type molybdenum dioxide catalysis and hydroxylammonium salt react the method directly preparing aniline, the method comprises the steps: to 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 molybdenum dioxide catalyzer that Carbon Materials supports (is called for short MoO
2/ C), active ingredient MoO in this catalyzer
2account for 3 ~ 15% of catalyzer total mass.The selectivity of aniline of the present invention can reach 99%, and yield can reach 54%, and catalyst preparation process is simple, with low cost, 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 molybdenum 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 catalyzer that the method uses is Ni, Cu, Ce, V, Ti metal catalyst that titanium-silicon molecular sieve TS-1 supports, ammoniacal liquor is as aminating agent, and hydrogen peroxide is as oxygenant (patent publication No.: CN101906045).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, this seminar proposes with solubility vanadic salts (vanadylic sulfate, ammonium meta-vanadate, sodium metavanadate) as catalyzer in patent 200510020505, 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, but soluble vanadium salt catalyst is expensive, cost is higher, thus also limit the industrial application of the method.
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, use the molybdenum dioxide catalyzer that a kind of Carbon Materials supports, this catalyzer can catalysis benzene and hydroxylammonium salt react a step and obtains aniline and have 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 the hydroxylammonium salt of the catalysis of loading type molybdenum dioxide react the method directly preparing aniline, 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 molybdenum dioxide catalyzer that Carbon Materials supports (is called for short MoO
2/ C), active ingredient MoO in this catalyzer
2account for 3 ~ 15% of catalyzer total mass.
Described hydroxylammonium salt is oxammonium hydrochloride or oxammonium sulfate.
Carbon Materials supports a preparation method for molybdenum dioxide catalyzer, comprises the steps:
Ammonium molybdate 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 molybdenum dioxide catalyzer (MoO
2/ C);
Wherein, material proportion is mol ratio ammonium molybdate: sucrose=1:10 ~ 40, and every 60 ml deionized water add 0.5 ~ 2.0mmol ammonium molybdate.
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 54%, 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 product separation 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, preparation process is simple, easy to operate, and environmental friendliness, 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
MoO
2the preparation of/C-1# catalyzer: by 1.0g (0.8mmol) ammonium molybdate 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, SeteramSetsys16/18 thermal analyzer carries out thermogravimetric (TG) analysis to catalyzer, and in known prepared catalyzer, the mass percentage of active ingredient is 6% as calculated.Due to this catalyst activity component MoO
2loading less, in the XRD spectra of Fig. 1, on the steamed bun peak of unformed charcoal, therefore only there is a more weak diffraction peak, correspond to standard substance MoO through this diffraction peak of comparison
2the strongest diffraction peak of (PDF 00-001-0615).
Embodiment 2
MoO
2the preparation of/C-2# catalyzer: preparation process is identical with embodiment 1, difference is that the amount of added ammonium molybdate is 0.59g (0.5mmol), obtains MoO in catalyzer through thermogravimetric (TG) analytical calculation
2mass percentage be 4%.
Embodiment 3
MoO
2the preparation of/C-3# catalyzer: preparation process is identical with embodiment 1, difference is that the amount of added ammonium molybdate is 1.5g (1.2mmol), obtains MoO in catalyzer through thermogravimetric (TG) analytical calculation
2mass percentage be 10%.
Embodiment 4
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 0.1gMoO 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 5
Concrete reaction process is identical with embodiment 4, and difference is that used catalyst is MoO
2/ C-2# catalyzer.
Embodiment 6
Concrete reaction process is identical with embodiment 4, and difference is that used catalyst is MoO
2/ C-3# catalyzer.
Embodiment 7
MoO
2the reusability of/C-1# catalyzer: reaction process is identical with embodiment 4, difference is that used catalyst is the MoO that embodiment 4 reacts rear recovery
2/ C-1# catalyzer.
Embodiment 8
Benzene reacts the reaction of directly aniline processed with oxammonium sulfate: concrete reaction process is identical with embodiment 4 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 4-8.
Unaccomplished matter of the present invention is known technology.
Claims (2)
1. the benzene of loading type molybdenum dioxide catalysis and hydroxylammonium salt react the method directly preparing aniline, 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 molybdenum dioxide catalyzer that Carbon Materials supports (is called for short MoO
2/ C), active ingredient MoO in this catalyzer
2account for 3 ~ 15% of catalyzer total mass;
Described Carbon Materials supports the preparation method of molybdenum dioxide catalyzer, comprises the steps:
Ammonium molybdate 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 molybdenum dioxide catalyzer (MoO
2/ C);
Wherein, material proportion is mol ratio ammonium molybdate: sucrose=1:10 ~ 40, and every 60 ml deionized water add 0.5 ~ 2.0mmol ammonium molybdate.
2. the benzene of loading type molybdenum dioxide catalysis as claimed in claim 1 and hydroxylammonium salt react the method directly preparing aniline, and it is characterized by described hydroxylammonium salt is oxammonium hydrochloride or oxammonium sulfate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410751457.6A CN104402736B (en) | 2014-12-10 | 2014-12-10 | Benzene and the hydroxylammonium salt of the catalysis of a kind of loading type molybdenum dioxide react the method directly preparing aniline |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410751457.6A CN104402736B (en) | 2014-12-10 | 2014-12-10 | Benzene and the hydroxylammonium salt of the catalysis of a kind of loading type molybdenum dioxide react the method directly preparing aniline |
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| Publication Number | Publication Date |
|---|---|
| CN104402736A CN104402736A (en) | 2015-03-11 |
| CN104402736B true CN104402736B (en) | 2016-04-06 |
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| CN105523907B (en) * | 2015-12-14 | 2019-01-01 | 河北工业大学 | A method of cyclohexanone is directly prepared by benzene |
| CN106268615B (en) * | 2016-08-05 | 2018-09-04 | 北京工业大学 | A kind of MoO2/CaSO4Composite material and its application |
| CN109574853A (en) * | 2017-09-29 | 2019-04-05 | 普济生物科技（台州）有限公司 | For synthesizing method, catalyst and its application of amino benzenes compounds |
| CN108355642A (en) * | 2018-03-29 | 2018-08-03 | 长春工业大学 | A kind of catalyst and preparation method and usage for benzene direct aminatin aniline |
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| US4059628A (en) * | 1974-12-26 | 1977-11-22 | E. I. Du Pont De Nemours And Company | Preparation of aromatic amines |
| RU2259350C2 (en) * | 2003-07-14 | 2005-08-27 | Открытое акционерное общество "Пигмент" | Method for preparing aniline and/or n-methylaniline and catalyst for its |
| CN101837293A (en) * | 2010-05-07 | 2010-09-22 | 河北工业大学 | Catalyst for synthesizing methylaniline from methylbenzene by one step and preparation method thereof |
| CN102716753A (en) * | 2012-06-08 | 2012-10-10 | 华电电力科学研究院 | Catalyst for low-temperature selective catalytic reduction of nitric oxide and preparation method of catalyst |
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| US4059628A (en) * | 1974-12-26 | 1977-11-22 | E. I. Du Pont De Nemours And Company | Preparation of aromatic amines |
| RU2259350C2 (en) * | 2003-07-14 | 2005-08-27 | Открытое акционерное общество "Пигмент" | Method for preparing aniline and/or n-methylaniline and catalyst for its |
| CN101837293A (en) * | 2010-05-07 | 2010-09-22 | 河北工业大学 | Catalyst for synthesizing methylaniline from methylbenzene by one step and preparation method thereof |
| CN102716753A (en) * | 2012-06-08 | 2012-10-10 | 华电电力科学研究院 | Catalyst for low-temperature selective catalytic reduction of nitric oxide and preparation method of catalyst |
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| One-pot synthesis of cersols from toluene and hydroxylamine catalyzed by ammonium molybdate;Dongsheng Zhang,et al.;《Catalysis Communications》;20110402;第12卷(第12期);1109-1112 * |
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