CN101695668B - Synthesizing method of MCM-41-TiCuAl catalyst and preparation method of 1-naphthol - Google Patents
Synthesizing method of MCM-41-TiCuAl catalyst and preparation method of 1-naphthol Download PDFInfo
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Abstract
The invention provides a synthesizing method of an MCM-41-TiCuAl catalyst and a preparation method of 1-naphthol. The synthesizing method of the MCM-41-TiCuAl catalyst comprises the following steps: dissolving cetyl trimethyl ammonium bromide and sodium silicate in hot water to obtain a clear solution, adjusting the pH value to be 7 by utilizing dilute sulphuric acid, sequentially dropping a titanium trichloride solution and a cupric nitrate solution into the clear solution, then adjusting the pH value to be 9.0-9.5 by utilizing ammonia, and finally dropping a sodium aluminate solution; stirring, reacting by heating, naturally cooling and washing, then drying at room temperature to obtain catalyst raw powder; raising the temperature to 550 DEG C at the speed of 1 DEG C/min in a muffle to roast for 5h, and obtaining the catalyst along with the natural cooling of the muffle. The preparation method of 1-naphthol comprises the following steps: mixing naphthalene, a solvent and the catalyst, heating and raising the temperature to 50-80 DEG C, and finishing dropping H2O2 within 2-4h, wherein the reaction time is 2-18h; cooling, then filtering out the catalyst and recycling the solvent; adding aqueous alkali to adjust the pH value to be 11, filtering and recycling the naphthalene; adjusting the pH value of the filtrate to be 4, extracting and drying by utilizing ethyl acetate, and distilling in vacuum to obtain the 1-naphthol. The invention has little pollution, short line, simple operation, easy preparation of the catalyst and easy realization of industrial production.
Description
Technical field
The invention belongs to the preparation method of aromatic ring class hydroxyl substituted compound, proposed the synthetic method of MCM-41-TiCuAl catalyst and the preparation method of 1-naphthols especially.
Background technology
The 1-naphthols claims alpha-Naphthol again, is the intermediate of important organic synthesis fine chemicals, is widely used in the aspects such as synthetic and textile auxiliary of medicine, agricultural chemicals, chiral ligand, spices.
The main production method of 1-naphthols has three kinds.1, sulfonated alkali fusion method.With the naphthalene is raw material, through concentrated acid sulfonation, hydrolysis, neutralization, alkali fusion, acidifying, refining.Defectives such as this technology exists complex manufacturing, long flow path, equipment corrosion is serious, the three wastes are many, environmental pollution is big.2, the different third naphthalene method.With naphthalene and propylene is raw material, makes the 1-isopropyl naphthalene through the catalysis isopropylation, makes 1-isopropyl naphthalene peroxide through oxidation again, and last acid decomposition obtains 1-naphthols and acetone.This explained hereafter complex process, parameter control requires high, and a large amount of peroxide causes the security of technology relatively poor, and catalyst is difficult to solve, and only has minority offshore company to adopt this process route.3, naphthylamines Hydrolyze method.With the nitrated 1-nitronaphthalene of making of naphthalene, be reduced to naphthalidine, be the 1-naphthols with naphthalidine HTHP acidic hydrolysis again.This method synthetic route is long, the three wastes are many, equipment investment is big.
The research report that the synthetic 1-naphthols of some newer direct hydroxylatings is also arranged in the document, as: utilize that beautiful little Ke Yinhan is mould, mushroom metabolism such as Bacillus cercus ATCC14579, green alga Chlorella and streptomyces griseus NRRL 8090 generate the 1-naphthols.By bio-transformation the naphthalene hydroxylating is generated in the 1-naphthols process, the toluene oxygenase has embodied higher activity and selectivity.But because naphthols has very big toxicity to biological bacteria or enzyme, cause the conversion ratio of naphthalene low and reaction solution concentration is very low, industrial production efficiency is low.Directly the catalytic hydroxylation synthetic method is the method that recent two decades has the industrialization potentiality most, is a kind of green synthesis process.Basic principle is under the effect of catalyst and oxidant, makes the directly synthetic naphthols of naphthalene one one-step hydroxylation reaction.Catalyst mainly contains two big classes, and a class is metal oxide or its alloy, and another kind of is metallorganic.There is the problem of poor selectivity in the former, the peroxidating phenomenon often occurs.The latter prepares complexity, and the catalyst cost is higher.Research tendency in recent years mainly concentrates on seeks that selectivity is good, operating condition is simple, low-cost catalyst.
Summary of the invention
At existing 1-naphthols preparation technology's deficiency, the present invention proposes the synthetic method of MCM-41-TiCuAl catalyst and the preparation method of 1-naphthols especially,, directly naphthalene one one-step hydroxylation reaction is prepared the 1-naphthols with molecular sieve catalysts that is.Molecular sieve MCM-41 is that people study a more class important materials recently.It has the pore passage structure that six sides arrange in order, regular one dimension intermediate pore size, and the aperture can change at 1.6～10nm, synthetic wide ranges, skeleton can in very large range be regulated.The MCM-41 molecular sieve has high surface, high absorption property and acid more weak characteristics, and the back of often mixing is as catalysis material, carrier material and adsorbent etc.The present invention has prepared the molecular sieve (being called MCM-41-TiCuAl) of a certain amount of titanium that mixes, copper, aluminum metal element as catalyst, and catalyst is by the sol-gel Hydrothermal Preparation.
The present invention adopts acetonitrile as solvent, and MCM-41-TiCuAl is a catalyst, with H
2O
2Be hydroxylating reagent, successfully prepared the 1-naphthols by direct hydroxylating of one step of naphthalene.With low cost being easy to get of catalyst raw material of adopting, simple to operate, overcome the shortcoming that former 1-naphthols production technology is polluted big, long flow path, complex process, poor stability simultaneously, be green production process preferably, be easy to industrialization.
Concrete technical scheme of the present invention is as follows:
The synthetic method of MCM-41-TiCuAl catalyst, step is:
Softex kw and sodium metasilicate be dissolved in obtain settled solution in the hot water, transfer pH=7 with dilute sulfuric acid, successively titanium trichloride aqueous solution and copper nitrate aqueous solution are added drop-wise in the above-mentioned solution, transfer pH to 9.0～9.5 with ammoniacal liquor again, drip sodium aluminate aqueous solution at last; After stirring, the mixed sols that obtains is changed in the autoclave of inner liner polytetrafluoroethylene,, make it naturally cool to room temperature in 120-180 ℃ of hydro-thermal reaction 24-72h; Wash respectively to there not being chlorion with deionized water and absolute ethyl alcohol, drying at room temperature obtains catalyst raw powder; Former powder speed with 1 ℃/min in Muffle furnace is warming up to 550 ℃ of roasting 5h, cools off naturally with stove, obtains catalyst;
Each raw material ratio of quality and the number of copies is:
Nine water sodium metasilicate: softex kw: titanium trichloride: nitrate trihydrate copper: sodium aluminate=1: 0.5: 0.05-0.17: 0.04-0.2: 0.01-0.04.
With the catalyst MCM-41-TiCuAl of the present invention's preparation, prepare the method for 1-naphthols, step is as follows:
After naphthalene, solvent, MCM-41-TiCuAl catalyst mix, heat to 50-80 ℃, in 2-4h, drip H
2O
2, reaction time 2～18h; Cooling back elimination catalyst reclaims solvent; Add aqueous slkali and transfer pH to 11, filtered and recycled naphthalene; Filtrate is transferred pH to 4, uses ethyl acetate extraction, after the extract drying, obtains the 1-naphthols through vacuum distillation;
The proportioning of reaction mass is:
Naphthalene: H
2O
2Mol ratio=1: 1～6;
Naphthalene: acetonitrile ratio of quality and the number of copies=1: 8～12;
Naphthalene: MCM-41-TiCuAl catalyst quality portion rate=1: 0.1～0.3.
The present invention proposes a kind of new preparation process of 1-naphthols, and the employing acetonitrile is a solvent, with H
2O
2Be hydroxylating reagent, under MCM-41-TiCuAl catalysis, the direct one-step method of naphthalene be converted into the 1-naphthols.Compared following advantage with existing processes: pollute little, route short, simple to operate, catalyst is easy to preparation, be easy to industrial production.
The specific embodiment
1. Preparation of catalysts:
Embodiment 1:
In the 250mL four-hole bottle of thermometer, agitating device is housed, add 7.10g CTAB, nine hydrated sodium silicate 14.20g and 80mL deionized water, stirring heats up down obtains settled solution.Behind 1M dilute sulfuric acid accent pH=7, the aqueous solution 20mL that will contain titanium trichloride 2.30g under the strong agitation is added drop-wise in the above-mentioned solution.Drip the aqueous solution 25mL that contains nitrate trihydrate copper 0.60g copper nitrate then, transfer pH to 9.0～9.5 with ammoniacal liquor again, add the aqueous solution 15mL that contains sodium aluminate 0.12g at last.The mixed sols that obtains is changed in the autoclave of inner liner polytetrafluoroethylene, in 120 ℃ of hydro-thermal reaction 72h.Reaction makes it naturally cool to room temperature, centrifugation after finishing.Wash respectively three times with deionized water and absolute ethyl alcohol, detect no chlorion with silver nitrate, drying at room temperature obtains catalyst raw powder.Former powder speed with 1 ℃/min in Muffle furnace is warming up to 550 ℃ of roasting 5h, naturally cool off with stove, obtain the MCM-41-TiCuAl catalyst A, the titanium in the sample, copper, aluminium content are determined that by ICP wherein each element wt ratio is titanium 15.4%, copper 3.3%, aluminium 0.8% in the catalyst.
Embodiment 2:
According to said method, change the amount that adds metal ion, the aqueous solution 20mL that contains titanium trichloride 1.54g, the aqueous solution 20mL that contains nitrate trihydrate copper 2.41g copper nitrate, the aqueous solution 15mL that contains sodium aluminate 0.25g at 180 ℃ of hydro-thermal reaction 24h, gets the MCM-41-TiCuAl catalyst B, titanium in the sample, copper, aluminium content are determined that by ICP wherein each element wt ratio is titanium 9.2%, copper 13.3%, aluminium 1.4% in the catalyst.
Embodiment 3:
According to said method, change the amount that adds metal ion, the aqueous solution 20mL that contains titanium trichloride 0.77g, the aqueous solution 20mL that contains nitrate trihydrate copper 1.23g copper nitrate, the aqueous solution 15mL that contains sodium aluminate 0.41g at 160 ℃ of hydro-thermal reaction 40h, gets MCM-41-TiCuAl catalyst C, titanium in the sample, copper, aluminium content are determined that by ICP wherein each element wt ratio is titanium 6.4%, copper 8.3%, aluminium 2.8% in the catalyst.
2.1-naphthols preparation:
Embodiment 4:
In the 500mL four-hole bottle of thermometer, agitating device is housed, add naphthalene 25.6g (0.2mol), acetonitrile 300mL, catalyst A 2.56g.Heat to 65 ℃, drip 30% H
2O
268mL (0.6mol), time spent 2h, insulation reaction 8h.Cooling back elimination catalyst reclaims acetonitrile.Add dilute alkaline soln and transfer pH to 11, filtered and recycled naphthalene 15.2g.Mother liquor is transferred pH to 4, with ethyl acetate 2 * 150mL extraction.Reclaim ethyl acetate, get 1-naphthols 5.1g through vacuum distillation again, 95.3～96.1 ℃ of fusing points.Naphthalene conversion ratio 40.6%, 1-naphthols selectivity 43.6%.
Embodiment 5:
In the 500mL four-hole bottle of thermometer, agitating device is housed, add naphthalene 25.6g (0.2mol), acetonitrile 260mL, catalyst A 7.68g.Heat to 80 ℃, drip 30% H
2O
268mL (0.6mol), time spent 2h, insulation reaction 2h.Cooling back elimination catalyst reclaims acetonitrile.Add dilute alkaline soln and transfer pH to 11, filtered and recycled naphthalene 17.3g.Mother liquor is transferred pH to 4, with ethyl acetate 2 * 150mL extraction.Reclaim ethyl acetate, get 1-naphthols 4.2g through vacuum distillation again, 95.2～96.0 ℃ of fusing points.Naphthalene conversion ratio 32.4%, 1-naphthols selectivity 45.0%.
Embodiment 6:
In the 250mL four-hole bottle of thermometer, agitating device is housed, add naphthalene 25.6g (0.1mol), acetonitrile 330mL, catalyst B 2.56g.Heat to 50 ℃, drip 30% H
2O
268mL (0.6mol), time spent 4h, insulation reaction 18h.Cooling back elimination catalyst reclaims acetonitrile.Add dilute alkaline soln and transfer pH to 11, filtered and recycled naphthalene 16.2g.Mother liquor is transferred pH to 4, with ethyl acetate 2 * 150mL extraction.Reclaim ethyl acetate, get 1-naphthols 4.9g through vacuum distillation again, 95.3～96.1 ℃ of fusing points.Naphthalene conversion ratio 36.7%, 1-naphthols selectivity 46.3%.
Embodiment 7:
In the 500mL four-hole bottle of thermometer, agitating device is housed, add naphthalene 12.8g (0.1mol), acetonitrile 190mL, catalyst C 2.56g.Heat to 60 ℃, drip 30% H
2O
268mL (0.6mol), time spent 2h, insulation reaction 12h.Cooling back elimination catalyst reclaims acetonitrile.Add dilute alkaline soln and transfer pH to 11, filtered and recycled naphthalene 7.0g.Mother liquor is transferred pH to 4, with ethyl acetate 2 * 100mL extraction.Reclaim ethyl acetate, get 1-naphthols 2.7g through vacuum distillation again, 95.2～96.1 ℃ of fusing points.Naphthalene conversion ratio 45.3%, 1-naphthols selectivity 41.4%.
The present invention is not limited to the technology described in the embodiment, and its description is illustrative, and nonrestrictive.Authority of the present invention is limited by claim, based on present technique field personnel according to the present invention can change, technology related to the present invention that method such as reorganization obtains, all within protection scope of the present invention.
Claims (2)
1.MCM-41-TiCuAl the synthetic method of catalyst is characterized in that step is as follows:
Softex kw and nine water sodium metasilicate are dissolved in obtain settled solution in the hot water, transfer pH=7 with dilute sulfuric acid, successively titanium trichloride aqueous solution and nitrate trihydrate copper liquor are added drop-wise in the above-mentioned solution, transfer pH to 9.0～9.5 with ammoniacal liquor again, drip sodium aluminate aqueous solution at last; After stirring, the mixed sols that obtains is changed in the autoclave of inner liner polytetrafluoroethylene,, make it naturally cool to room temperature in 120-180 ℃ of hydro-thermal reaction 24-72h; Wash respectively to there not being chlorion with deionized water and absolute ethyl alcohol, drying at room temperature obtains catalyst raw powder; Former powder speed with 1 ℃/min in Muffle furnace is warming up to 550 ℃ of roasting 5h, cools off naturally with stove, obtains catalyst;
Each raw material ratio of quality and the number of copies is:
Nine water sodium metasilicate: softex kw: titanium trichloride: nitrate trihydrate copper: sodium aluminate=1: 0.5: 0.05-0.17: 0.04-0.2: 0.01-0.04.
2.1-the preparation method of naphthols is characterized in that: after naphthalene, solvent acetonitrile, MCM-41-TiCuAl catalyst mix, heat to 50-80 ℃, in 2-4h, drip H
2O
2, reaction time 2～18h; Cooling back elimination catalyst reclaims solvent; Add aqueous slkali and transfer pH to 11, filtered and recycled naphthalene; Filtrate is transferred pH to 4, uses ethyl acetate extraction, after the extract drying, obtains the 1-naphthols through vacuum distillation;
The proportioning of reaction mass is:
Naphthalene: H
2O
2Mol ratio=1: 1～6;
Naphthalene: acetonitrile ratio of quality and the number of copies=1: 8～12;
Naphthalene: MCM-41-TiCuAl catalyst quality portion rate=1: 0.1～0.3.
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Effective date of registration: 20201119 Address after: 226321, Jiangsu, Nantong province two Tongzhou District town industrial concentration area Patentee after: Nantong New Fengwei Machinery Technology Co.,Ltd. Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92, Tianjin University Patentee before: Tianjin University |