CN103055918B - Preparation method for supported solid-acid catalyst for synthesising 2-isonaphthol via one-step hydroxylation of naphthalene - Google Patents
Preparation method for supported solid-acid catalyst for synthesising 2-isonaphthol via one-step hydroxylation of naphthalene Download PDFInfo
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Abstract
The invention discloses a preparation method for a supported solid-acid catalyst for synthesising 2-isonaphthol via the one-step hydroxylation of naphthalene, belonging to the technical field of supported solid-acid catalysts, wherein via the technical scheme of soaking a supporter in a solution containing an auxiliary constituent precursor in a vacuum condition, vibrating and drying in a low-temperature water bath, and calcining for 1-3 hours at 400-600 DEG C at first, and then soaking the calcined powder in the solution containing an auxiliary constituent precursor in a vacuum condition, vibrating and drying in the low-temperature water bath, and baking in an airflow at 110-300 DEG C, a solid-acid catalyst which is adjustable in surface acidity and high in the dispersibility of active constituents is prepared. With the adoption of the method, the various problems existing in the prior art are effectively solved, the conversion rate of naphthalene and the selectivity of 2-isonaphthol are greatly increased, and good effects are obtained.
Description
Technical field
The invention belongs to load-type solid acid catalyst technical field, be applied to polycyclic aromatic hydrocarbon compounds (PAHs) hydroxylating, that be specifically related to is a kind of exclusive preparation method synthesizing the solid acid catalyst of beta naphthal for naphthalene one one-step hydroxylation.
Background technology
Beta naphthal has another name called betanaphthol, ethyl naphthol or 2 hydroxy naphthalene, is important Organic Chemicals and synthetic intermediate, and the dyestuff directly synthesized by it, pigment variety reach kind more than 130, dyestuff intermediate more than 20.Also be widely used in medicine, agricultural chemicals, rubber chemicals, spices, leather tanning, textile auxiliary and dressing agent etc.
The traditional processing technology of beta naphthal has: 1, sulfonated alkali fusion method.Sulfonated alkali fusion method is current domestic and international industrialized main method, and Technical comparing is ripe.Take naphthalene as raw material, obtain beta naphthal through processes such as high temperature sulfonation, neutralization, alkali fusion, acidifying, distillations.2, isopropyl naphthalene method.This technique for raw material, makes 2-isopropyl naphthalene through isopropylation with naphthalene and propylene, then makes 2-isopropyl naphthalene peroxide through oxidation, and last acid is decomposed and obtained beta naphthal and acetone.3, Hydrolyze method.Wherein be mainly chloronaphthalene method.Obtain chloronaphthalene with naphthalene chlorination, under catalyst stannous chloride and potassium chloride exist, reaction temperature 800 DEG C, is hydrolyzed in the duct with water vapour and obtains.These three kinds of techniques are multistep reaction, and atom utilization is low, and selectivity of product is poor, produce multiple a large amount of secondary refuse; Use a large amount of soda acid, higher to the requirement of the material of reactor, the three wastes of generation are many, and environmental pollution is serious.
In order to improve the production technology of beta naphthal, many researchers are constantly developing new technology.The green syt research of naphthols becomes research and development focus.At present, the green synthesis method of beta naphthal mainly contains: 1, thorugh biologic engineering method.Being transformed by biology makes naphthalene hydroxylating generate in the process of beta naphthal, and toluene oxygenase embodies higher activity and selectivity.But because naphthols has very large toxicity to biological bacteria or enzyme, make biological enzyme agent inactivation, the conversion per pass of naphthalene is low, and industrial production efficiency is low.2, direct catalytic hydroxylation synthetic method.It is the method having industrialization potential in the last few years most, and general principle is under the effect of catalyst and oxidant, makes naphthalene one one-step hydroxylation reaction directly synthesize naphthols.The method solves from the source that product synthesizes that naphthols building-up process is complicated, discharge of wastewater is many, be difficult to the problem of administering.Take hydrogen peroxide as the reaction process of oxidant, the emphasis that because its technological process is simple, water byproduct is nontoxic, environmental protection becomes research and development now.
In naphthalene one one-step hydroxylation synthesis beta naphthal technique, mainly contain acid catalyzed process, metal oxide oxidation catalyst method, wherein: acid catalyzed process be main with liquid superacid HF for catalyst, this shortcoming making this technique have homogeneous catalytic reaction self to be difficult to overcome: selectivity of product is poor, separation and recovery of catalyst is difficult, serious to equipment corrosion, technique is difficult to continuous seepage.In addition, the acidity of catalyst is excessively strong, and make the naphthols generated be generated polyhydroxy naphthalene by further hydroxylation, selectivity of product is poor.
Metal oxide oxidation catalyst method is the catalyst using solid acid as hydroxylating, as described the research of spinel-type ferrous acid magnesium as naphthalene hydroxylation catalysts in document Yang Hui fine jade " chemical industry in Jiangsu Province ", under the optimum process condition of its report, poor catalyst activity, the total recovery of naphthols is only up to 12.7%, and document Tang Ji proposes in " Chemical Manufacture and technology in " a kind of by active component Fe forever
2o
3be carried on high specific surface carrier γ-Al
2o
3preparation method, compared with pure metal oxides catalyst, active component Fe
2o
3utilization rate increase, but m (Fe
2o
3)/m (γ-Al
2o
3) >250%, active component bad dispersibility, atom utilization is still lower, in addition, with Fe
2o
3as the active component of naphthalene hydroxylation catalysts, the naphthols of generation is easily generated polyhydroxy naphthalene by further hydroxylation, and selectivity of product is poor.
Summary of the invention
The object of the present invention is to provide a kind of active component acid amount moderate, and easily by the preparation method of load-type solid acid catalyst regulated and controled, especially the catalyst that active component high dispersive, catalytic activity are high and cheap is prepared, when this serial solid acid catalyst prepares beta naphthal for naphthalene hydroxylating, improve the conversion ratio of naphthalene and the selective of beta naphthal.
For achieving the above object, the technical solution used in the present invention is as follows.
For a preparation method for the load-type solid acid catalyst of naphthalene one one-step hydroxylation synthesis beta naphthal, it is characterized in that, adopt infusion process, specifically comprise the following steps:
(1) catalyst carrier is vacuumized, start timing when vacuum reaches 630-730mmHg, vacuumize 1-5h;
(2) adjuvant component presoma is joined dissolve in isopyknic water with pore volume, and add a certain amount of surfactant, stir, obtain maceration extract;
(3) be added drop-wise in the carrier of the step (1) keeping vacuum state by disposable for the maceration extract in step (2), after the suspension obtained by dipping stirs 1-5h, then atmospheric low-temperature water-bath concussion is dry, by dried powder after 400-600 DEG C of calcining 1-3h, obtain the carrier containing auxiliary agent oxide, grind to form powder;
(4) powder that grinding obtains is reached 630-730mmHg in vacuum and vacuumize 1-5h;
(5) active component is joined with the isopyknic water of step (3) gained powder pore volume in dissolve, and add a certain amount of surfactant, stir, obtain maceration extract;
(6) maceration extract in step (5) is added drop-wise to rapidly in the powder keeping vacuum state in step (4), stirs, then after atmospheric low-temperature water-bath concussion drying, in the air stream of 110 DEG C-300 DEG C, dry 1-3h, obtain load-type solid acid catalyst.
Catalyst carrier described in step (1) is Al
2o
3series, HY, LAY, 13X, ZSM-5/50H, ZSM-5/80H, ZSM-5/100H, diatomite or sepiolite etc., the acidity that can select from these carriers further and naphthalene hydroxylating system match, pore size and naphthalene (0.58nm) and the close carrier of beta naphthal (0.70nm) molecular diameter size.
Adjuvant component presoma described in step (2) is nitrate, possesses certain Acidity of Aikalinity and can regulating catalyst acid amount, and cost is lower, the nitrate of preferred IA, IIA, VIIIB, IB, IIB, and auxiliary agent presoma consumption is the 1-25% of carrier quality.
One or more more preferably in cobalt nitrate, zinc nitrate, copper nitrate, magnesium nitrate, calcium nitrate, lithium nitrate etc. of auxiliary agent presoma described in step (2).
Step (2) and the surfactant described in step (5) are diethanol amine, triethanolamine, aliphatic alcohol polyethenoxy (3) ether (are called for short: AEO
3), aliphatic alcohol polyethenoxy (9) ether (be called for short: AEO
9), the mixing of one or more in neopelex, odium stearate, lauryl sodium sulfate, tween, oleic acid, consumption is the 1%-5% of maceration extract volume, step (2) and the surfactant described in step (5) can identical also can be different.
Drying means described in step (3) is low temperature water-bath concussion method, bath temperature 20-40 DEG C, when can reduce water evaporation, and the probability of subsiding of carrier aperture.
Active component described in step (5) is one or more in zirconium sulfate, zirconium oxychloride, and the consumption of active component is the 5-60% of carrier quality; Preferably sulfuric acid zirconium, can regulate the content of catalyst activity component crystallizes water further by the bake out temperature of regulating step (5), thus realizes the regulation and control to acidity of catalyst, as catalyst Z rSO4.3H
2the acidity of O/HY is weak, low conversion rate, poor selectivity; Catalyst Z rSO4.H
2the acidity of O/HY is moderate, and conversion ratio is high, and beta naphthal yield is high; When temperature is 700 degree, the complete water of zirconium sulfate, becomes ZrO
2/ HY, acid centre disappears, and beta naphthal conversion ratio is 0.Another technical scheme of the present invention, is characterized in that, compare technique scheme, does not comprise step (2)-(4).
When preferably adopting separately zirconium sulfate, its consumption is 5%-55% of carrier quality; Adopt zirconium sulfate and cobalt nitrate time, its consumption be respectively carrier quality 5%-55%, 3%-15%; When adopting zirconium sulfate, cobalt nitrate and magnesium nitrate, its consumption is respectively 5%-55%, 3%-15%, 1%-7% of carrier quality.
The inventive method, the advantage of this catalyst is:
1), in the present invention, the carrier of preparing of catalyst has acid Modulatory character and carrier aperture Modulatory character as required: catalyst to prepare support acidity large, the activity of catalyst is high, and catalyst choice can be poor; Catalyst to prepare support acidity little, catalytic activity is weak, and conversion per pass is little, and feedstock circulation utilizes often, makes its cost high; Carrier aperture is large, and target product can not be shifted out in time, easily secondary reaction occurs, by-product object height; Carrier aperture is little, and product easily blocks, catalyst easy in inactivation, and the life-span is short;
2) in the present invention, the auxiliary agent of catalyst---metal oxide utilizes its atomic radius size, achieves and the mating of carrier aperture: the bore dia that need reduce carrier, will select large metal oxide supported of diameter as far as possible; The relatively little carrier in aperture then selects the little metal oxide of diameter to unload, and finally realizes matching of metal oxide and carrier aperture.Such as: the atomic radius for modulation molecular sieve bore diameter and acid metal Fe, Cu, Ca, Mg, Sn is respectively: 1.241A °, 1.278A ° 1.974A °, 1.599A °, 1.45A °; The aperture of common molecular sieve 3a, 4A, 5A, ZSM-5,10X, 13X, Y, MCM-41 is: 3A °, 4A °, 5A °, 5.5A ° 9A °, 10A °, 7.4A °, 16-100A °
The Acidity of Aikalinity of metal oxide and the Acidity of Aikalinity of carrier match the allotment realized catalyst acid alkalescence, and the neutral or alkaline metal oxide of highly acid carrier is adjuvant component, such as: common neutral metal oxide: ZrO
2, TiO
2, alkaline metal oxide: MgO, CaO etc.; Less acidic support then preferred low acidic metal oxide unloads, such as: common low acidic metal oxide: Fe
2o
3, V
2o
5deng.
3) in the present invention, by the active component of regulating catalyst---the zirconates crystallization water yield of the band crystallization water number, achieve acidity of catalyst and catalytic activity and optionally regulate and control, it is weak that active component contains the acidity of catalyst of 3 crystallizations water, low conversion rate, poor selectivity; Active component is moderate containing the acidity of catalyst of 1 crystallization water, and conversion ratio is high, and beta naphthal yield is high, the complete dehydration of active component, and after becoming zirconia, the acid centre of catalyst disappears, and beta naphthal conversion ratio is 0.
In addition, in the present invention, the active constituent of catalyst and the load capacity of auxiliary agent directly affect the Acidity of Aikalinity of catalyst, and with the catalytic activity of catalyst and selective relevant.
The application's patent finally achieves catalyst pore size and naphthalene and naphthols molecular diameter and matches, and catalyst acid alkalescence adapts with naphthalene hydroxylating, reaches the best catalytic activity of naphthalene hydroxylating and selective.Instant invention overcomes existing Fe system solid acid catalyst active component bad dispersibility, utilization rate is low, the naphthalene low conversion rate that acidity of catalyst is strong etc. causes, the shortcoming of poor selectivity.
Accompanying drawing explanation
Fig. 1: in carrier HY and embodiment 1-4, the XRD of catalyst characterizes
(a)HY；(b)ZrSO4.nH
2O/HY；(c)ZrSO4.mH
2O/HY；(d)CoO-ZrSO4.mH
2O/HY；(e)CoO-MgO-ZrSO4.mH
2O/HY。
Detailed description of the invention
Below in conjunction with detailed description of the invention, the invention will be further described.
Embodiment 1 catalyst Z rSO4.nH
2the preparation (n=3) of O/HY
Accurately taking 1g carrier HY transfers in bottle,suction, degassed dehydration under vacuum 650mmHg; Precise zirconium sulfate 0.5g simultaneously, molten in the deionized water of 6ML, add the surfactant A EO-9 of liquor capacity 3%, be configured to maceration extract, maceration extract is transferred in the funnel being arranged on one with bottle,suction, vacuumize after 2h until catalyst carrier, open funnel switch, the maceration extract prepared is joined rapidly in carrier, stirring 2h by flooding the suspension obtained, shaking at 40 DEG C to water evaporate to dryness, till powder is dry and cracked by low temperature water bath chader, by the powder grinding obtained, after drying 2h at 110 DEG C, obtain load-type solid acid catalyst ZrSO4.nH
2o/HY, is designated as CAT-1, and its XRD characterizes Fig. 1-(b) seen in accompanying drawing explanation
Embodiment 2 catalyst Z rSO4.mH
2the preparation (m=1) of O/HY
Accurately taking 1g carrier HY transfers in bottle,suction, degassed dehydration under vacuum 650mmHg; Precise zirconium sulfate 0.5g simultaneously, molten in the deionized water of 6ML, add the surfactant A EO-9 of liquor capacity 3%, be configured to maceration extract, maceration extract is transferred in the funnel being arranged on one with bottle,suction, vacuumize after 2h until catalyst carrier, open funnel switch, the maceration extract prepared is joined rapidly in carrier, stirring 2h by flooding the suspension obtained, shaking at 40 DEG C to water evaporate to dryness, till powder is dry and cracked by low temperature water bath chader, by the powder grinding obtained, after drying 2h at 200 DEG C, obtain load-type solid acid catalyst ZrSO4.mH
2o/HY, is designated as CAT-2 (m ≠ n), and its XRD characterizes Fig. 1-(c) seen in accompanying drawing explanation.
Embodiment 3 CATALYST Co O-ZrSO4.mH
2the preparation of O/HY (m=1)
Accurately taking 1g carrier HY transfers in bottle,suction, degassed dehydration under vacuum 650mmHg, precise cobalt nitrate 0.07g is molten in the deionized water of 6ML simultaneously, add the surfactant A EO-9 of liquor capacity 1%, be configured to maceration extract, maceration extract is transferred in the funnel being arranged on one with bottle,suction, vacuumize after 1h until catalyst carrier, open funnel switch, the maceration extract prepared is joined rapidly in carrier, 2h is stirred by flooding the suspension obtained, shake at 40 DEG C to water evaporate to dryness by low temperature water bath chader, till powder is dry and cracked, by the powder grinding obtained, after put in Muffle furnace 400 DEG C calcining 2h, prepare the solid acid catalyst that load has auxiliary agent.
Transfer to after load being had the catalyst powder of auxiliary agent to grind suction filtration flat in, degassed dehydration under vacuum 670mmHg; Precise zirconium sulfate 0.5g simultaneously, molten in the deionized water of 6ML, the surfactant A EO-9 adding liquor capacity 3% is configured to maceration extract, maceration extract is transferred in funnel, vacuumize after 2.5h until catalyst carrier, open funnel switch, the maceration extract prepared is joined rapidly in carrier, 2h is stirred by flooding the suspension obtained, shake at 40 DEG C to water evaporate to dryness by low temperature water bath chader, powder is dry and cracked, by the powder grinding obtained, obtains load-type solid acid catalyst CoO-ZrSO4.mH after drying 2h at 200 DEG C
2o/HY, is designated as CAT-3, and its XRD characterizes Fig. 1-(d) seen in accompanying drawing explanation.
Embodiment 4 CATALYST Co O-MgO-ZrSO4.mH
2the preparation of O/HY (m=1)
Accurately taking 1g carrier HY transfers in bottle,suction, degassed dehydration under vacuum 670mmHg, precise cobalt nitrate 0.07g simultaneously, magnesium nitrate 0.03g is molten in the deionized water of 6ML, add the surfactant A EO-9 of liquor capacity 2%, be configured to maceration extract, maceration extract is transferred in the funnel being arranged on one with bottle,suction, vacuumize after 1.5h until catalyst carrier, open funnel switch, the maceration extract prepared is joined rapidly in carrier, 2h is stirred by flooding the suspension obtained, shake at 40 DEG C to water evaporate to dryness by low temperature water bath chader, till powder is dry and cracked, by the powder grinding obtained, after put in Muffle furnace 450 DEG C calcining 2h, prepare the solid acid catalyst that load has auxiliary agent.
Transfer to after load being had the catalyst powder of auxiliary agent to grind suction filtration flat in, degassed dehydration under vacuum 690mmHg; Precise zirconium sulfate 0.5g simultaneously, molten in the deionized water of 6ML, the surfactant A EO-9 adding liquor capacity 3% is configured to maceration extract, maceration extract is transferred in funnel, vacuumize after 3h until catalyst carrier, open funnel switch, the maceration extract prepared is joined rapidly in carrier, 2h is stirred by flooding the suspension obtained, shake at 40 DEG C to water evaporate to dryness by low temperature water bath chader, powder is dry and cracked, by the powder grinding obtained, obtains load-type solid acid catalyst CoO-MgO-ZrSO4.mH after drying 2h at 200 DEG C
2o/HY, is designated as CAT-4, and its XRD characterizes Fig. 1-(e) seen in accompanying drawing explanation.
The above-mentioned catalyst sample prepared is used for naphthalene hydroxylating, and reaction condition is as follows:
Wherein: naphthalene 3g, catalyst 0.6g, 30% hydrogen peroxide 3.27g, acetone 25ml, reaction time 7h, temperature 55 DEG C, after reaction terminates, suction filtration, reclaims catalyst, after reactant liquor removes acetone and water, add diethyl ether dissolving, ether is for gas chromatographic analysis, and adopt external standard method to calculate the conversion ratio of naphthalene and selective, naphthalene hydroxylating the results are shown in Table 1.
The catalytic performance of the solid acid catalyst of table 1 difference composition
With the metal oxide of bibliographical information, the catalyst of load metal oxide is compared, in the present invention, the diffraction maximum of 4 kinds of catalyst of XRD sign (see accompanying drawing 1) is consistent with the position of carrier HY and shape, there is not active component zirconium sulfate, CoO, the diffraction maximum of MgO, this illustrates that catalyst activity component and auxiliary agent effectively can be dispersed in carrier surface, active component utilization rate is high, the acidity of catalyst is easy to modulation, associative list 1 catalyst performance test data is known, this catalyst series and naphthalene hydroxylating system adapt to more, naphthalene conversion ratio, the selective data being all better than bibliographical information of beta naphthal.
The present invention is not limited to the technology described in embodiment, and its description is illustrative, and nonrestrictive.Invention authority of the present invention limited by claim, can change based on the art personnel, recombinate according to the present invention.
Claims (3)
1., for a preparation method for the load-type solid acid catalyst of naphthalene one one-step hydroxylation synthesis beta naphthal, it is characterized in that, adopt infusion process, specifically comprise the following steps:
(1) catalyst carrier is vacuumized, start timing when vacuum reaches 630-730mmHg, vacuumize 1-5h;
(2) adjuvant component presoma is joined dissolve in isopyknic water with pore volume, and add a certain amount of surfactant, stir, obtain maceration extract;
(3) be added drop-wise in the carrier of the step (1) keeping vacuum state by disposable for the maceration extract in step (2), after the suspension obtained by dipping stirs 1-5h, then atmospheric low-temperature water-bath concussion is dry, by dried powder after 400-600 DEG C of calcining 1-3h, obtain the carrier containing auxiliary agent oxide, grind to form powder;
(4) powder that grinding obtains is reached 630-730mmHg in vacuum and vacuumize 1-5h;
(5) active component is joined with the isopyknic water of step (3) gained powder pore volume in dissolve, and add a certain amount of surfactant, stir, obtain maceration extract;
(6) maceration extract in step (5) is added drop-wise to rapidly in the powder keeping vacuum state in step (4), stir, then, after atmospheric low-temperature water-bath concussion drying, in the air stream of 200 DEG C, dry 1-3h, obtain load-type solid acid catalyst;
Catalyst carrier described in step (1) is HY;
Adjuvant component presoma described in step (2) is nitrate, be II A or/and the nitrate of VIII B, auxiliary agent presoma consumption is the 1-25% of carrier quality;
Step (2) and the surfactant described in step (5) are diethanol amine, triethanolamine, aliphatic alcohol polyethenoxy (3) ether (are called for short: AEO
3), aliphatic alcohol polyethenoxy (9) ether (be called for short: AEO
9), the mixing of one or more in neopelex, odium stearate, lauryl sodium sulfate, tween, oleic acid, consumption is the 1%-5% of maceration extract volume;
Drying means described in step (3) is low temperature water-bath concussion method, bath temperature 20-40 DEG C;
Active component described in step (5) is zirconium sulfate, and the consumption of active component is the 5-60% of carrier quality.
2., according to the preparation method of claim 1, it is characterized in that, adopt zirconium sulfate and cobalt nitrate time, its consumption be respectively carrier quality 5%-55%, 3%-15%.
3. the load-type solid acid catalyst for naphthalene one one-step hydroxylation synthesis beta naphthal prepared by method according to claim 1.
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| CN104888859A (en) * | 2015-05-13 | 2015-09-09 | 安徽金邦医药化工有限公司 | Silicon dioxide loaded fluorapatite composite solid acid catalyst and preparation method thereof |
| CN104888747A (en) * | 2015-05-13 | 2015-09-09 | 安徽金邦医药化工有限公司 | Magnetic composite solid acid catalyst and preparation method thereof |
| CN104888790A (en) * | 2015-05-13 | 2015-09-09 | 安徽金邦医药化工有限公司 | Cobaltous sulfate modified silicon dioxide mesoporous composite solid acid catalyst, and preparation method thereof |
| CN106040266B (en) * | 2016-06-21 | 2019-01-15 | 中国科学院福建物质结构研究所 | A kind of solid acid catalyst and its preparation method and application |
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| EP1024129A2 (en) * | 1999-01-27 | 2000-08-02 | President of Kobe University a government agency of Japan | Method of manufacturing phenol by direct oxidation of benzene |
| CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
| CN1724163A (en) * | 2005-07-13 | 2006-01-25 | 北京化工大学 | Preparation for high dispersing, amorphous, high efficient novel desulfate catalyst |
| CN101440021A (en) * | 2008-09-12 | 2009-05-27 | 华东师范大学 | Method for preparing phenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1024129A2 (en) * | 1999-01-27 | 2000-08-02 | President of Kobe University a government agency of Japan | Method of manufacturing phenol by direct oxidation of benzene |
| CN1613559A (en) * | 2004-09-28 | 2005-05-11 | 北京化工大学 | Preparation for hydrophobic solid acid catalyst |
| CN1724163A (en) * | 2005-07-13 | 2006-01-25 | 北京化工大学 | Preparation for high dispersing, amorphous, high efficient novel desulfate catalyst |
| CN101440021A (en) * | 2008-09-12 | 2009-05-27 | 华东师范大学 | Method for preparing phenol |
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