CN103420424A - Preparation of rod-shaped nano tungsten trioxide and technology of catalytic synthesis of adipic acid therethrough - Google Patents
Preparation of rod-shaped nano tungsten trioxide and technology of catalytic synthesis of adipic acid therethrough Download PDFInfo
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Abstract
The invention provides a method for hydro-thermal synthesis of rod-shaped nano tungsten trioxide using p-aminobenzoic acid as an adjuvant, as well as a method for catalytic synthesis of adipic acid. According to the invention, tungstate is used as tungsten source, p-aminobenzoic acid is used as a morphological control agent, and the rod-shaped nano tungsten trioxide is obtained through hydro-thermal synthesis; then, hydrogen peroxide is used as an oxidant, rod-shaped nano tungsten trioxide is used as a catalyst for catalytic synthesis of adipic acid. The method is mainly characterized in two points: firstly, a new approach is adopted to synthesize the nano tungsten trioxide; secondly, adipic acid can be obtained through catalytic synthesis via the synthesized catalyst cleanly and efficiently (the yield of adipic acid can reach 51.92%-82.20%) without an organic solvent and a phase transfer catalyst.
Description
Technical field
The invention belongs to chemosynthesis technical field, relate in particular to the technology of rod-like nano tungstic oxide catalyzer, preparation method and catalyzed oxidation synthesizing adipic acid thereof.
Background technology
Hexanodioic acid is a kind of important organic dibasic acid, and main application is synthon, i.e. nylon-66.The consumption of annual hexanodioic acid is very large, and at present, industrial synthesizing adipic acid is generally still applied traditional production technique, with dense HNO
3As oxygenant, this technique is very large to the harm of environment.The shortcoming of traditional processing technology mainly is, the oxygenant of use is the strong dense HNO of corrodibility
3, and can a large amount of N of discharge in production process
2O, and N
2O gas is a kind of energy broken ring ozonosphere and promotes the greenhouse gases that acid rain forms.Therefore, finding that a kind of green is clean, the synthetic method of environment-friendly high-efficiency, is the key of current hexanodioic acid synthesising process research.
In 20 end of the centurys, people just start the tungsten sill as catalyzer for the building-up reactions of hexanodioic acid, and have obtained extraordinary catalytic effect.Up to the present, the tungsten-based catalyst of reporting mainly contains Na
2WO
4, H
2WO
4With phospho-wolframic acid etc.People's reportings such as Sato (Science 1998,281 (5383), 1646) are with Na
2WO
4For catalyzer, [CH
3(n-C
8H
17)
3N] HSO
4For consisting of phase-transferring agent, the system of 30% catalytic oxidation of hydrogen peroxide tetrahydrobenzene synthesizing adipic acid.The yield of hexanodioic acid is up to 93%, but consisting of phase-transferring agent [CH used
3(n-C
8H
17)
3N] HSO
4Synthetic route comparatively complicated, and catalyzer exists with " false liquid phase " form, recycles very difficult.
CN200710133233.9 discloses a kind of method of oxidation synthesis of adipic acid by epoxy cyclohexane in May, 2008.This invention is under the condition without organic solvent, and take tungsten, molybdenum multi-metal oxygen hydrochlorate is catalyzer, and aqueous hydrogen peroxide solution is made oxygenant, the catalysis oxidation synthesis of adipic acid by epoxy cyclohexane.Temperature of reaction 60 ~ 105
oC, reaction times 6 ~ 20 h, the yield of hexanodioic acid can reach 46.9% ~ 83.2%.In this invention, the reaction substrate epoxy cyclohexane is a kind of intermediate, and its source is more restricted with respect to tetrahydrobenzene, and the complicated component of catalyzer, not easy to be recycled.
CN200810062524.8 discloses a kind of method of preparing hexane diacid by liquid-phase catalytic oxidation of cyclohexanol in November, 2008.This invention is with phospho-wolframic acid 1-butyl-3-methylimidazole salt [bmim]
3PMo
12O
40, phospho-molybdic acid 1-butyl-3-methylimidazole salt [bmim]
3PMo
12O
40And molybdovanaphosphoric acid 1-butyl-3-methylimidazole salt [bmim]
3+xPMo
12-xV
xO
40(x=1 ~ 3) etc., [bmim] represents 1-butyl-3-Methylimidazole positively charged ion.Avoided the use of phase-transfer catalyst and auxiliary agent in this reaction system, but the synthetic complexity of catalyzer is not easy to be recycled, and its catalytic performance is lower, active limited.
In sum, the tungsten sill is synthetic for hexanodioic acid, and its catalytic performance is comparative superiority all, but the recycling of catalyzer is the difficult point of this respect research always.Catalyzer often is present in reaction system with the form of " false liquid phase ", and this has brought very large difficulty to the Separation and Recovery of post catalyst reaction.2005, Yan Song etc. (Chinese Tungsten Industry 2005,20 (2), 33) not with an organic solvent, acid ligand and consisting of phase-transferring agent, with 30%H
2O
2For oxygenant, WO
3Make catalyst oxidation tetrahydrobenzene synthesizing adipic acid, the productive rate of hexanodioic acid is 75.4%, and selectivity reaches 99.8%.In literary composition, propose at WO
3During for catalyzer, can generate peroxide wolframic acid H with hydroperoxidation
2WO
2(O
2)
2, be dissolved in the organic phase tetrahydrobenzene, play the effect of phase transition.And after the reaction end, due to H
2O
2Be consumed WO
3Separate out, can at an easy rate catalyzer be separated from reaction system.But productive rate phase wolframic acid and the phospho-wolframic acid of hexanodioic acid are lower, need further research to improve the productive rate of its hexanodioic acid.
Summary of the invention
In order to overcome above-mentioned the deficiencies in the prior art, the invention provides a kind of simple method for preparing rod-like nano tungstic oxide catalyzer, the catalyzer of gained has less particle diameter and higher catalytic activity.At consumption under less condition, clean, catalysis tetrahydrobenzene synthesizing adipic acid efficiently.Wherein, the building-up process of catalyzer has been carried out to preliminary amplification, found that its composition, pattern etc. change little, illustrated that its synthetic method stability is high, reproducible.
The object of the present invention is to provide a kind of rod-like nano tungstic oxide catalyzer that synthesizing adipic acid is there is to high catalytic activity.
Another object of the present invention is to provide the preparation method of above-mentioned catalyzer.
One of technical scheme of the present invention is to provide a kind of rod-like nano tungstic oxide catalyzer of synthesizing adipic acid, and its preparation method is achieved through the following technical solutions:
Take 1 ~ 30 g tungstate and add in 20 ~ 250 mL water, dropwise add metering than being the HCl(1 of 1:1 ~ 20 mL under the condition of magnetic agitation).After stirring, add 1 ~ 10 g pattern adjusting control agent, then stir 20 min ~ 2 h, pour mixture into reactor.Under 100 ~ 280 ℃, react 10 ~ 40 h in air dry oven.To obtain second alcohol and water repetitive scrubbing for material, suction filtration, drying, obtain final product.
In technique scheme, the tungstate used is a kind of for sodium wolframate, ammonium paratungstate, ammonium tungstate or phospho-wolframic acid, and the pattern adjusting control agent is para-amino benzoic acid, finally obtains rod-like nano tungstic oxide catalyzer.
Two of technical scheme of the present invention is that a kind of rod-like nano tungstic oxide is clean, the method for efficient catalytic synthesizing adipic acid, its building-up reactions is undertaken by step once: to the catalyzer, 20 ~ 60 mL hydrogen peroxide that add above-mentioned synthetic method to synthesize in reaction vessel, stir 2 ~ 30 min under room temperature, the tetrahydrobenzene and a certain amount of acid ligand that add again calculated amount, high degree of agitation, rise to 90 ℃ of 2 ~ 50 h that reflux after 73 ℃ of heating 1 ~ 10h.After reaction, suction filtration obtains transparent liquid, and it,, 0 ℃ of lower standing over night, is separated out to a large amount of white crystals.After suction filtration, drying, the product obtained is weighed, and calculate yield.The catalyzer of preparation is used for to the hexanodioic acid building-up reactions.
In technique scheme, the acid ligand of using is oxalic acid, phosphoric acid, sulfuric acid, citric acid or salicylic a kind of.
The accompanying drawing explanation
The electron micrograph that Fig. 1 is rod-like nano tungstic oxide of the present invention.(a) scanning electronic microscope (SEM) photo; (b) transmission electron microscope (TEM) photo.The comparing result that Fig. 2 is each embodiment synthesizing adipic acid yield of the present invention.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated.These embodiment are interpreted as only for the present invention is described, is not used in and limits the scope of the invention.After the content of having read the present invention's record, the various changes of the present invention being made based on principle of the present invention or modification fall into the claims in the present invention book limited range equally.
Embodiment 1
6.6 g Na
2WO
4 .2H
2O (0.02 mol) adds in 50 mL water, dropwise adds metering than being the HCl(9 mL of 1:1 under the condition of magnetic agitation).After stirring, add 5.48 g(0.04 mol) para-amino benzoic acid, then stir 0.5 h, pour mixture into reactor.Under 180 ℃, reaction 24 h in air dry oven.To obtain second alcohol and water repetitive scrubbing for material, suction filtration, drying, obtain final product.
By the above-mentioned synthetic catalyzer of 0.0356 g, 0.1 g oxalic acid, 4.1 ml 30%H
2O
2Add in the 10mL reaction vessel with 8 mmol tetrahydrobenzene, this reactor is placed in to 90 ℃ of reaction 12 h of baking oven, add a certain amount of acetone after reaction, the mixed solution centrifugation is removed to catalyzer, get supernatant liquor and revolve steaming, air-dry, obtain product.Product is weighed, calculate yield, the results are shown in accompanying drawing 2.
Embodiment 2
Accurately take 33 g Na
2WO
4 .2H
2O (0.1 mol) adds in 250 mL water, dropwise adds metering than being the HCl(45 mL of 1:1 under the condition of magnetic agitation).After stirring, add 27.4 g(0.2 mol) para-amino benzoic acid, then stir 0.5 h, pour mixture into reactor.Under 180 ℃, reaction 24 h in air dry oven.To obtain second alcohol and water repetitive scrubbing for material, suction filtration, drying, obtain final product.
Add the above-mentioned synthetic catalyzer of 1.5 mmol, 0.4 mol 30%H in reaction vessel
2O
2, 0.12 mol oxalic acid, stir 15 min under room temperature, then add the tetrahydrobenzene of calculated amount, and high degree of agitation rises to 90 ℃ of 10 h that reflux after 73 ℃ of heating 2 h.After reaction, suction filtration obtains transparent liquid, and it,, 0 ℃ of lower standing over night, is separated out to a large amount of white crystals.After suction filtration, drying, the product obtained is weighed, and calculate yield, the results are shown in accompanying drawing 2.
Embodiment 3
Accurately take 33 g Na
2WO
4 .2H
2O (0.1 mol) adds in 250 mL water, dropwise adds metering than being the HCl(45 mL of 1:1 under the condition of magnetic agitation).After stirring, add 27.4 g(0.2 mol) para-amino benzoic acid, then stir 0.5 h, pour mixture into reactor.Under 180 ℃, reaction 24 h in air dry oven.To obtain second alcohol and water repetitive scrubbing for material, suction filtration, drying, obtain final product.
Add the above-mentioned synthetic catalyzer of 1.5 mmol, 0.4 mol 30%H in reaction vessel
2O
2, 0.196 g sulfuric acid, 0.0161 g phosphoric acid, stir 15 min under room temperature, then add the tetrahydrobenzene of calculated amount, and high degree of agitation rises to 90 ℃ of 10 h that reflux after 73 ℃ of heating 2 h.After reaction, suction filtration obtains transparent liquid, and it,, 0 ℃ of lower standing over night, is separated out to a large amount of white crystals.After suction filtration, drying, the product obtained is weighed, and calculate yield, the results are shown in accompanying drawing 2.
By accompanying drawing 2, can be found out, the rod-like nano tungstic oxide catalyzer that the present invention is prepared, in the situation that add small amount, to synthesizing adipic acid, reaction has higher catalytic activity.Wherein, take the rod-like nano tungstic oxide as catalyzer, oxalic acid is acid ligand, and the yield of hexanodioic acid is 82.20%.Oxalic acid is a kind of weak acid, all smaller to the hazardness of the corrodibility of instrument and environment, than strong acid nitric acid, is a kind of everybody general receptible acid ligand.And, find, between our selected oxalate ligand and tungstic oxide catalyzer, certain part effect is arranged in the comparative result of acid ligand from embodiment, this effect can improve the yield of hexanodioic acid.The preparation process of high reactivity rod-like nano tungstic oxide catalyzer provided by the invention is simple, can be dispersed in well in the reaction system of catalyzed oxidation synthesizing adipic acid.In addition, rod-like nano tungstic oxide catalyzer of the present invention, under the condition without organic solvent, consisting of phase-transferring agent, can clean, efficient catalysis tetrahydrobenzene synthesizing adipic acid.
Claims (7)
1. the method for a synthetic bar-shaped nano tungsten trioxide, is characterized in that 1 ~ 30 g tungstate adds in 20 ~ 250 mL water, dropwise adds metering than being the HCl(1 of 1:1 ~ 20 mL under the condition of magnetic agitation).After stirring, add 1 ~ 10 g pattern adjusting control agent, then stir 20 min ~ 2 h, pour mixture into reactor.Under 100 ~ 280 ℃, react 10 ~ 40 h in air dry oven.To obtain second alcohol and water repetitive scrubbing for material, suction filtration, drying, obtain final product.
2. the method for clean, the efficient catalytic synthesizing adipic acid of a rod-like nano tungstic oxide, it is characterized in that: to the catalyzer, 20 ~ 60 mL hydrogen peroxide that add above-mentioned synthetic method to synthesize in reaction vessel, stir 2 ~ 30 min under room temperature, the tetrahydrobenzene and a certain amount of acid ligand that add again calculated amount, high degree of agitation, rise to 90 ℃ of 2 ~ 50 h that reflux after 73 ℃ of heating 1 ~ 10h.After reaction, suction filtration obtains transparent liquid, and it,, 0 ℃ of lower standing over night, is separated out to a large amount of white crystals.After suction filtration, drying, the product obtained is weighed, and calculate yield.
3. the method for a kind of synthetic bar-shaped nano tungsten trioxide according to claim 1, it is characterized in that: the pattern adjusting control agent is para-amino benzoic acid.
4. the method for a kind of synthetic bar-shaped nano tungsten trioxide according to claim 1, it is characterized in that: tungstate is a kind of of sodium wolframate, ammonium paratungstate, ammonium tungstate or phospho-wolframic acid.
5. the method for clean, the efficient catalytic synthesizing adipic acid of a kind of rod-like nano tungstic oxide according to claim 2, it is characterized in that: catalyzer is the rod-like nano tungstic oxide in claim 1, and its diameter is about 10 ~ 20 nm.
6. the method for clean, the efficient catalytic synthesizing adipic acid of a kind of rod-like nano tungstic oxide according to claim 2, it is characterized in that: right to use requires the catalyzer described in 1, take hydrogen peroxide as oxygenant, after 73 ℃ of heating 1 ~ 10h, rise to catalysis tetrahydrobenzene synthesizing adipic acid under 90 ℃ of back flow reaction 2 ~ 50 h.
7. the method for clean, the efficient catalytic synthesizing adipic acid of a kind of rod-like nano tungstic oxide according to claim 2, it is characterized in that: acid ligand is oxalic acid, phosphoric acid, sulfuric acid, citric acid or salicylic a kind of.
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| CN104843793A (en) * | 2015-05-22 | 2015-08-19 | 重庆大学 | Method for preparing hydrous tungsten oxide nanorod array without template |
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| CN105388138A (en) * | 2015-12-23 | 2016-03-09 | 哈尔滨工业大学 | Optical measurement method based on tungsten oxide serving as ethyl alcohol gas sensing material |
| CN105819514A (en) * | 2016-03-01 | 2016-08-03 | 富通集团有限公司 | Chromic material, preparation method thereof, and early warning cable sheath |
| CN107055619B (en) * | 2017-03-27 | 2018-08-24 | 浙江大学 | A kind of multilevel hierarchy WO3And preparation method thereof |
| CN107055617A (en) * | 2017-04-05 | 2017-08-18 | 新疆师范高等专科学校 | A kind of preparation method for the molybdenum tungsten nano composite oxide degraded for Dye Adsorption |
| CN107115859A (en) * | 2017-04-05 | 2017-09-01 | 新疆师范高等专科学校 | The preparation method of tungsten trioxide nano crystalline substance photochemical catalyst |
| CN108862389A (en) * | 2017-05-16 | 2018-11-23 | 中国科学院上海硅酸盐研究所 | A kind of high-performance tungsten oxide nano-powder and its preparation method and application |
| CN108745341A (en) * | 2018-06-14 | 2018-11-06 | 深圳技术大学（筹） | A kind of preparation method for being catalyzed the tungstic acid of light degradation organic matter |
| CN108745341B (en) * | 2018-06-14 | 2021-01-15 | 深圳技术大学 | Preparation method of tungsten trioxide for catalyzing photodegradation of organic matters |
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