CN105536832A - Method for preparing mesoporous niobium phosphate catalyst and application of mesoporous niobium phosphate catalyst in preparation of isosorbitol from sorbitol - Google Patents

Method for preparing mesoporous niobium phosphate catalyst and application of mesoporous niobium phosphate catalyst in preparation of isosorbitol from sorbitol Download PDF

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CN105536832A
CN105536832A CN201510918916.XA CN201510918916A CN105536832A CN 105536832 A CN105536832 A CN 105536832A CN 201510918916 A CN201510918916 A CN 201510918916A CN 105536832 A CN105536832 A CN 105536832A
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catalyst
mesoporous
preparation
isobide
phosphate
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CN105536832B (en
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于波
丁万昱
刘世民
柴卫平
文斌
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Dalian Jiaotong University
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Dalian Jiaotong University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems

Abstract

The invention discloses a method for preparing a mesoporous niobium phosphate catalyst and an application of the mesoporous niobium phosphate catalyst in preparation of isosorbitol from sorbitol. The mesoporous niobium phosphate catalyst is synthesized by adopting a soft template surfactant assisted hydrothermal method; with utilization of the catalyst, a sorbitol dehydration reaction can be performed at lower temperature, the conversion rate of sorbitol can reach up to 100%, and the isosorbide selectivity is more than or equal to 50%. The catalyst has the advantages of good stability, easy synthesis, reproducibility, controllable acid amount and the like.

Description

The preparation method of mesoporous phosphate niobium catalyst and the application in sorbierite isobide thereof
Technical field
The present invention relates to the preparation of mesoporous phosphate niobium catalyst and the application in sorbierite isobide.Belong to catalytic chemistry and field of chemical engineering.Relate to the intersection of biomass energy, nano material and catalytic chemistry and integrated, being widening biomass resource utilization field, is also the transformation to traditional catalyst, to the further investigation of the nano effect essence in heterogeneous catalytic reaction.
Background technology
Living beings, due to its recyclability, aboundresources and highly functionalized, become the focus of 21st century catalytic field research.Current research both domestic and external lays particular emphasis on catalyzed conversion living beings and derivative preparing liquid fuel thereof and high valuable chemicals.From Atom economy analysis, synthesis bulk chemical and fine chemicals are of great significance making full use of this regenerated resources tool of living beings.
Isobide (isosorbide) is important biomass-based material, is widely used in the fields such as medicine, surfactant, plastics and polymer.Isobide is the anhydro derivatives of D-glucitol, is excellent depressor and the diuretics for the treatment of encephalic supercharging disease in medical.After isobide dehydration, hydroxyl becomes ehter bond, and it is fat-soluble increases greatly, absorbs immediately after oral, is a kind of effective oral dehydration and diuresis medicine of permeability.Because isobide does not have metabolism substantially, its dehydration and to reduce intracranial pressure effect definite, pharmacokinetics is simple, better tolerance, cardiovascular system, kidney and liver function are had no side effect and record in American Pharmacopeia and Pharmacopeia of Japan as medicine, substitutes the intravenous administration such as sweet mellow wine and be widely used in clinical.Isobide is also for the synthesis of antianginal drug Isosorbide Mononitrate and ISDN.
Isobide industrially has chiral centre and rigid structure because of it and has special purposes at Material Field, is widely used in the field such as electronics, national defence.Isobide can directly be used in the isosorbide modified PETG of commercial resin (PET), substitute with isosorbide moieties hot properties and the impact resistance that ethylene glycol can significantly improve PET, also reduce structure adaptability temperature and degree of crystallinity simultaneously.Except modified PET, isobide also has other many potential purposes in polymer industry.The 2-glycidyl ether-ether of isobide can replace bisphenol A epoxide resin, is used as the lashing wire of Food & Drink tank, and European Union announces to forbid within the border producing the plastic feeding bottle containing bisphenol-A in European Union from March, 2011.The chirality polyurethane derived by isobide, there are the good chemical market prospects of huge potential pharmacological interest and fractionation enantiomer, the copolymer of the isobide/Coronex of ad hoc structure can the excellent optical cable of production performance, be used as engineering plastics or have particular characteristic, the new polyesters material that price is suitable by controlling the arrangement exploitation of chiral molecules in side chain.
Traditional isobide synthetic route is the acid catalyzed sorbierite second dehydration reaction of the liquid such as sulfuric acid, phosphoric acid and P-TOLUENE SULFO ACID 99, although this homogenous process catalytic efficiency is higher, but reaction generates multiple dehydration accessory substance, complicated, the easy etching apparatus of product separation, increase production cost, be unfavorable for that heavy industrialization is applied.Be that the dehydration of catalyst has higher catalytic efficiency with liquid acid, but the harshness that the complexity of homogeneous reaction separation process and catalyst system and catalyzing require consersion unit, hinder further developing of isobide, and run counter to the sustainable development policy of green catalysis, and the application of solid acid catalyst solves this difficult problem, solid acid comprises HY, HZSM-5 molecular sieve, acid-exchange resin etc., solid acid can repeat regeneration with it, equipment corrosion and environmental pollution low, the features such as reactant and product are easily separated, become the main flow of acid catalyzed reaction development in recent years, research field is widened increasingly.
The domestic patent utilizing sorbierite to produce isobide is few, and comparatively representational is utilize the sorbierite dehydration on the solid acid catalysts such as imvite, molecular sieve, load phosphoric acid, metal phosphate, carried heteropoly acid, loading metal-salt.Above-mentioned catalyst is gas-solid reaction, and raw material is sorbitol aqueous solution, can lot of energy when this synthetic method is not only vaporized, and the acid centre of catalyst very easily runs off and causes catalysqt deactivation.
In sum, niobium phosphate solid acid catalyst is applied to sorbierite isobide catalytic field, has no patent report.
Summary of the invention
The present invention adopts composite shuttering surfactant PEO-PPOX-PEO triblock copolymer, also claims Pluronic, is called for short P123 (PEO 20pPO 70pEO 20), assisting alcohol-hydrothermal method one-step synthesis has meso-hole structure niobium phosphate solid acid catalyst, the specific area that meso-hole structure niobium phosphate solid acid catalyst utilizes mesoporous material high and pore volume, make it have more activated centre (B acid position), improve this catalyst activity and stability, this catalyst application is in sorbierite isobide reaction system simultaneously, and whole reaction is liquid-solid reaction, significantly can reduce energy consumption, raise the efficiency.
Technical scheme of the present invention is:
A preparation method for mesoporous phosphate niobium catalyst, comprises the following steps:
(1) at NbCl 5the aqueous solution in, drip phosphoric acid, stir, then add NH 3h 2o adjust ph to 3 ~ 6, filtering-depositing;
(2) precipitation and phosphoric acid are added in the P123 aqueous solution, stir;
(3) move in hydrothermal reaction kettle, at 40 ~ 80 DEG C, reacting 24 ~ 48h;
(4) sedimentation and filtration, washing, drying, at 300 ~ 800 DEG C in Muffle furnace roasting 4 ~ 8h.
As preferred technical scheme, in described step (1), stir 20 ~ 90min, rotating speed 300 ~ 800r/min.
As preferred technical scheme, in step (1), described NbCl 5with phosphoric acid quality than being 1:05 ~ 1:2, NbCl 5the mass percent of the aqueous solution is 10%.
As preferred technical scheme, in step (2), the mass ratio of described precipitation, P123, phosphoric acid is 1:2:0.01 ~ 1:10:2; The concentration of the described P123 aqueous solution is 5-15wt%; Stir 30 ~ 60min.
As preferred technical scheme, the mass fraction of described phosphoric acid is 85%.
The mesoporous phosphate niobium catalyst that the present invention also provides above-mentioned preparation method to obtain, described mesoporous phosphate niobium catalyst is undefined structure, and specific area is 110m 2/ g-190m 2/ g, particle diameter is 20 ~ 40nm.
The present invention also provides above-mentioned mesoporous phosphate niobium catalyst to prepare application in isobide in sorbierite system.
As preferred technical scheme, described application is with solid-state mesoporous niobium phosphate for catalyst, with liquid pure sorbitol for isobide prepared by raw material.
As preferred technical scheme, described application is that described liquid pure sorbitol and described solid-state mesoporous phosphate niobium catalyst add reactor with mass ratio 2:1 ~ 4:1, under nitrogen protection, is heated to 180 ~ 250 DEG C, and reaction 2-10h, is separated to obtain isobide.
The mesoporous phosphate niobium catalyst crystal formation SEM of preparation is characterized, as shown in Figure 1.As can be seen from Figure 1: catalyst particle size, at 20-40nm, has pore structure clearly.
The mesoporous phosphate niobium catalyst of preparation has been carried out nitrogen adsorption desorption detect, nitrogen adsorption desorption curve (inserting curve is the pore size distribution curve calculated by BJH method) as shown in Figure 2.As can be seen from Figure 2: the formation of typical TypeIV type adsorption desorption curve and hysteresis loop, proves that catalyst has meso-hole structure.Major part aperture, at 2-5nm, belongs to macropore range.
The mesoporous phosphate niobium catalyst of preparation has been carried out the infrared absorption test of pyridine, as shown in Figure 4, result display catalyst has two sour position: B acid position (1541cm -1absworption peak), L acid position (1450cm -1absworption peak).
The mesoporous phosphate niobium catalyst of the present invention is applied to tool in the reaction of sorbierite Dehydration isobide and has the following advantages:
(1) reaction efficiency is higher: sorbierite Dehydration isobide reaction conventional at present, and raw material sorbierite is the aqueous solution but not pure material, and this efficiency that classical inverse is answered is relatively low; And the reaction of applying mesoporous phosphate niobium catalyst is sorbierite is pure material, this makes this reaction efficiency higher.
(2) energy consumption of reaction is lower: the sorbierite Dehydration isobide reaction commonly used at present, and raw material sorbierite is for being the aqueous solution, and need rear for sorbitol aqueous solution gasification and solid acid catalyst to react, this will consume a large amount of energy and carry out pre-vaporized raw material; And the reaction of applying mesoporous phosphate niobium catalyst to be sorbierite be pure material and reaction is liquid-solid reaction, the energy of consumption is less, thus energy consumption is lower.
(3) reaction stability is good, unsuitable inactivation.Traditional sorbierite isobide reaction is mainly gas-solid reaction, has a large amount of water vapor adsorption at the acid centre (B acid position) of catalyst, therefore easy inactivation, the life-span of catalyst lower than 24h, generally at about 6h; And the present invention with mesoporous niobium phosphate for catalyst, reacted by sorbierite isobide and be mainly liquid-solid reaction, in reactant, there is no the participation of water, therefore not easy in inactivation.
Accompanying drawing explanation
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation:
Accompanying drawing 4 width of the present invention,
The mesoporous phosphate niobium catalyst SEM of Fig. 1 schemes;
The nitrogen adsorption desorption curve of the mesoporous phosphate niobium catalyst of Fig. 2;
The mesoporous niobium phosphate of Fig. 3 urges catalyst stability test result;
The mesoporous niobium phosphate of Fig. 4 urges the infrared absorption figure of catalyst pyridine.
Detailed description of the invention
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
Embodiment 1
Under magnetic agitation (mixing speed 600r/min), by 3.5gH 3pO 4solution (85wt%) is slowly added dropwise to NbCl 5(4gNbCl in solution 5be dissolved in 70mL deionized water), continue to stir 30min.Add NH 3h 2o is stabilized in 5 to pH value, and sedimentation and filtration washs.Gained precipitation adds 10%P123 aqueous solution 20mL, stirs 60min; Drip 1.2gNH 3h 2after O, moving to liner is in the stainless steel hydrothermal reaction kettle of polytetrafluoroethylene (PTFE), reacts 24h at 40 DEG C, subsequently further crystallization 24h at 75 DEG C.Sedimentation and filtration, washing, dry, at 450 DEG C in Muffle furnace roasting 6h, obtained mesoporous phosphate niobium catalyst.
Embodiment 2
Under magnetic agitation (mixing speed 600r/min), by 3.5gH 3pO 4solution (85wt%) is slowly added dropwise to NbCl 5(7gNbCl in solution 5with 70mL deionized water), continue to stir 30min.Add NH 3h 2o is stabilized in 4 to pH value, and sedimentation and filtration washs.Gained precipitation adds 10%P123 aqueous solution 20mL, to add quality be 2g mass fraction be 85% phosphoric acid solution, stir 30-60min and stir 60min; Drip 1.2gNH 3h 2after O, moving to liner is in the stainless steel hydrothermal reaction kettle of polytetrafluoroethylene (PTFE), reacts 48h at 40 DEG C, subsequently further crystallization 24h at 45 DEG C.Sedimentation and filtration, washing, dry, at 600 DEG C in Muffle furnace roasting 6h, obtained mesoporous phosphate niobium catalyst.
The stability test of embodiment 3 catalyst.
After catalyst drying embodiment 1 prepared, rejoin secondary response in reactor, so circulation five times.The results are shown in Figure 3 analyses known, after mesoporous phosphate niobium catalyst recycles five times, sorbierite conversion ratio and isobide is selective does not obviously reduce, keep constant, catalyst is without deactivation phenomenom.
Comparative example
By mesoporous phosphate niobium catalyst prepared by embodiment 1, embodiment 2, contrast with Amberlyst-15 catalyst (commercial catalysts).
Join in 50mL batch (-type) stainless steel cauldron under 0.4g sorbierite, 0.1g catalysts conditions, 230 DEG C of reaction 4h, reactant liquor is centrifugal, and liquid-like carries out liquid-phase chromatographic analysis.Sorbierite and product isobide adopt water generation high performance liquid chromatography to detect, differential (RI) detector temperature: 30 DEG C, ShodexSUGARSH1011 analytical column, column temperature: 75 DEG C, pure water is mobile phase (0.5mL/min), and measurement result is as follows:
Sorb alcohol conversion 85% under Amberlyst-15 catalyst condition, isobide selective 25%; And adopt the mesoporous phosphate niobium catalyst of embodiment 1, sorbierite conversion ratio 100%, isobide selective 47%; And adopt the mesoporous phosphate niobium catalyst of embodiment 2, sorbierite conversion ratio 100%, isobide selective 52%.

Claims (9)

1. the preparation method of mesoporous phosphate niobium catalyst, comprises the following steps:
(1) at NbCl 5in the aqueous solution, drip phosphoric acid, stir, then add NH 3h 2o adjust ph to 3 ~ 6, filtering-depositing;
(2) precipitation and phosphoric acid are added in PEO-PPOX-PEO triblock copolymer aqueous solution, stir;
(3) move in hydrothermal reaction kettle, at 40 ~ 80 DEG C, reacting 24 ~ 48h;
(4) sedimentation and filtration, washing, drying, at 300 ~ 800 DEG C in Muffle furnace roasting 4 ~ 8h.
2. preparation method according to claim 1, is characterized in that, in described step (1), stirs 20 ~ 90min, rotating speed 300 ~ 800r/min.
3. preparation method according to claim 1, is characterized in that, in step (1), and described NbCl 5with phosphoric acid quality than being 1:05 ~ 1:2, NbCl 5the mass percent of the aqueous solution is 5-15%.
4. preparation method according to claim 1, is characterized in that, in step (2), the mass ratio of described precipitation, PEO-PPOX-PEO triblock copolymer, phosphoric acid is 1:2:0.01 ~ 1:10:2; The concentration of described PEO-PPOX-PEO triblock copolymer aqueous solution is 5-15wt%; Stir 30 ~ 60min.
5. preparation method according to claim 1, is characterized in that, the mass fraction of described phosphoric acid is 85%.
6. the mesoporous phosphate niobium catalyst that obtains of preparation method described in claim 1-5 any one, it is characterized in that, described mesoporous phosphate niobium catalyst is undefined structure, and specific area is 110m 2/ g-190m 2/ g, particle diameter is 20 ~ 40nm.
7. mesoporous phosphate niobium catalyst described in claim 7 prepares the application in isobide in sorbierite system.
8. application according to claim 7, is characterized in that, with solid-state mesoporous niobium phosphate for catalyst, with liquid pure sorbitol for isobide prepared by raw material.
9. application according to claim 8, is characterized in that, described liquid pure sorbitol and described solid-state mesoporous niobium phosphate is added reactor with mass ratio 2:1 ~ 4:1, under nitrogen protection, is heated to 180 ~ 250 DEG C, and reaction 2-10h, is separated to obtain isobide.
CN201510918916.XA 2015-12-10 2015-12-10 The preparation method of mesoporous phosphate niobium catalyst and its application in sorbierite isobide Expired - Fee Related CN105536832B (en)

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CN114671883A (en) * 2022-05-07 2022-06-28 华东理工大学 Method for preparing isosorbide by dehydrating sorbitol under catalysis of niobium-based solid acid

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CN107473266A (en) * 2016-06-08 2017-12-15 中国石油化工股份有限公司 A kind of niobium phosphate Porous materials and its production and use
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CN106732701A (en) * 2017-01-11 2017-05-31 贵州大学 A kind of Fe2O3 doping niobium phosphate solid acid catalyst
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CN114671883A (en) * 2022-05-07 2022-06-28 华东理工大学 Method for preparing isosorbide by dehydrating sorbitol under catalysis of niobium-based solid acid

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