CN109433184A - A kind of SnO2/ MgAl-LDO solid base and the preparation method and application thereof - Google Patents

A kind of SnO2/ MgAl-LDO solid base and the preparation method and application thereof Download PDF

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CN109433184A
CN109433184A CN201811363420.0A CN201811363420A CN109433184A CN 109433184 A CN109433184 A CN 109433184A CN 201811363420 A CN201811363420 A CN 201811363420A CN 109433184 A CN109433184 A CN 109433184A
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sno
mgal
ldo
acetone
solid base
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CN109433184B (en
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李勇飞
王亚茹
刘跃进
余荣栋
付林
唐红娟
潘浪胜
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Xiangtan University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom

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Abstract

In conjunction with hydrotalcite induced hydrolysis and heat treatment again hydration method, the SnO with hydrotalcite structure is synthesized2(II)/MgAl-LDO solid base, for being catalyzed in 5 hydroxymethyl furfural and condensation of acetone reaction synthesis Aviation Fuel intermediate (E)-4- (5- methylol-2- furyl)-3- butene-2 -one, in 5 hydroxymethyl furfural, acetone, SnO2(II)/mass ratio of MgAl-LDO solid base 1:4.6:0.1,100 DEG C of reaction temperature, reaction 2 hours, obtain product yield 98.76%, acetone self condenses by-product yield less than 1%, use stannous chloride for tin source, preparation cost is low, and catalytic activity is high, stability is good, reusable.

Description

A kind of SnO2/ MgAl-LDO solid base and the preparation method and application thereof
Technical field
The invention belongs to field of fine chemical, it is related to preparing a kind of layered solid alkali SnO2/ MgAl-LDO is catalyzed 5- methylol The side of furfural synthesis Aviation Fuel intermediate (E)-4- (5- methylol-2- furyl)-3- butene-2 -one (hereinafter referred to as HAC) Method.
Background technique
The biomass energy category renewable carbon energy, it directly or indirectly derives from the photosynthesis of green plants, can convert For conventional solid-state, liquid and fuel gas.Biomass conversion can be carried out by biology, pyrolysis, enzyme or chemistry route, wherein changing The raw material sources of method are flexible extensively, and approach is related to directly being converted into biology with grain farmer crop starchy carbohydrate and triglycerides Ethyl alcohol or biodiesel.It converts by primary raw material of celluloses such as cauline leaf, agricultural crop straw, forestry residues, can not only expand It the crop species of bio-fuel, even more waste utilization and is good for the environment.Lignocellulosic and hemicellulose hydrolyze generation first Sugared (glucose, xylose, fructose etc.), then dehydration generates C under acidic catalyst5(furfural) and C6(5 hydroxymethyl furfural), however it is raw At these aldehyde by direct hydrogenation mode to obtain alkane octane number low.To meet the liquid that combustion in IC engine needs to obtain macromolecular Fluid fuel constructs C-C key by aldol reaction under acid or base catalysis and increases the macromolecular liquid fuel of carbochain as most Good selection.It can get C in acid or the 5 hydroxymethyl furfural and acetone of base catalysis different mol ratio9And C15Liquid alkane precursor, most Aviation fuel liquid alkane C can be obtained by open loop Hydro-deoxygenation-isomerization processing9 Alkane, key are related to 5- methylol The condensation reaction that furfural and acetone generate HAC is as follows:
The catalyst for being conventionally used to the reaction is mostly the homogeneous liquids alkali such as KOH, NaOH and ammonium hydroxide, there is pollution environment, corrosion Equipment and the problems such as separate difficulty with product.In recent years, it attracts attention for the solid acid of aldol reaction, base catalysis, it is main There are houghite, zeolite molecular sieve, composite oxides, amberlite (strong-base anion-exchange resin Amberlite IRA-900), the loaded catalysts such as MOFs, alkali or alkaline earth metal.The present invention is intended to provide a kind of preparation process it is simple, Inexpensively and the good solid base SnO of catalytic performance2/ MgAl-LDO is catalyzed 5 hydroxymethyl furfural and acetone aldol condensation prepares aviation Fuel intermediate HAC.Technical solution
A kind of SnO2(II)/MgAl-LDO solid base, it is characterized in that:
(1) SnO described in2(II) Mg, Al, Sn molar ratio 2.5 ~ 3.5:1:0.1 ~ 0.15 in/MgAl-LDO solid base；
(2) SnO described in2(II) in/MgAl-LDO solid base, SnO2It is dispersed in the hexagonal plate magnalium hydrotalcite of regular appearance On laminate, the SnO on neatly stone veneer is exposed to the open air2Nano microcrystalline is active site, in catalysis 5 hydroxymethyl furfural and acetone hydroxyl Aldehyde condensation reaction synthesis target product Aviation Fuel intermediate (E)-4- (5- methylol-2- furyl)-3- butene-2 -one (with Lower abbreviation HAC) in, acetone can be activated to lose α-H-shaped into nucleophilic carbanion intermediate well, then with another molecule 5- hydroxyl first Carbonyl carbon on base furfural carries out nucleophilic addition, forms new unsaturated carbon-carbon bond, obtains β-hydroxyl containing active α-H Base ketone, the beta-hydroxy ketone containing active α-H lose α, the beta unsaturated ketone that a molecular water forms more stable conjugated double bond structures again That is target product HAC, so that the SnO2(II)/MgAl-LDO solid base has high catalytic activity；
(3) SnO described in2(II)/MgAl-LDO solid base has hydrotalcite layered structure, 50 ~ 150nm of partial size, pore volume 0.2 ~0.9 cm3/ g, 30 ~ 130 m of specific surface area2/ g, basicity pKa=9 ~ 11.5 have 100 ~ 200 DEG C, 300 ~ 450 DEG C, 480 ~ 600 Three kinds of basic sites of weak, medium, strong in DEG C three different temperatures sections, SnO2Lacking oxygen and oxygen migration ability make it is described SnO2(II)/MgAl-LDO solid base catalyst has more low coordination oxygen, makes in catalyst, strong base concentrations all increased, Compared with simple magnalium hydrotalcite, increase specific surface area and in, strong basicity site, in catalysis 5 hydroxymethyl furfural and acetone Aldol reaction synthesizes in target product HAC, promotes the shape of the α-H carbanion intermediate and beta-hydroxy ketone on acetone At, while the presence in strong basicity site is more advantageous to intermediate C9Alcohol sloughs 1 hydrone water and forms target product HAC, so that institute The SnO stated2(II)/MgAl-LDO solid base catalyst has high selectivity；
2. SnO described in preparation 12(II)/MgAl-LDO solid base method, being different from existing co-precipitation is that element matches (Mg + Sn)/Al=2.8 ~ 3.2:1 or Mg/ (Sn+Al)=2.8 ~ 3.2:1 prepare tin same order elements part magnesium or aluminum for SnMgAl-LDH Method, but hydrotalcite induced hydrolysis and heat treatment hydration method again are combined, with SnCl2·2H2O is tin source, ammonium hydroxide is precipitating Agent, under salt-alkali environment of pH value 10 ± 0.5, so that SnCl2·2H2The SnO that O is hydrolyzed into2By oxygen-containing with hydrotalcite surface Functional group-OH is combined, to preferably be fixed in magnalium hydrotalcite carrier level, then obtains institute by 400 ~ 600 DEG C of roastings The SnO stated2(II)/MgAl-LDO, such Al3+It is not with Al2O3Object mutually exists, but Al3+Part occupies Mg in MgO lattice2+ Position, and MgO structure is not destroyed, do not form MgAl spinelle or MgO and MgAl2O4Two-phase is made with hydrotalcite structure SnO2(II)/MgAl-LDO, the specific steps are as follows:
Step 1: at room temperature according to the ratio of 2.5 ~ 3.5:1 of Mg, Al molar ratio, nine nitric hydrate magnesium and six water aluminum nitrates are same When be added in deionized water, forming concentration in 25 ~ 37 DEG C of stirring and dissolvings is that 0.48 ~ 0.55mol/L nitric acid magnalium salt-mixture is molten Liquid by the sodium hydroxide solution of obtained nitric acid magnalium mixing salt solution and 0.8 ~ 1.2mol/L while being slowly added into reactor In, mixed solution pH=10 ± 0.5 in reactor is controlled, 30 ~ 60min is stirred, white solid precipitating is obtained, by gained mixture Be transferred in the stainless steel water heating kettle of polytetrafluoroethyllining lining, 100 ~ 120 DEG C be aged 18 ~ for 24 hours, with deionized water filtering and washing To neutrality, filtering by filter cake in 100 ~ 120 DEG C of dry 8 ~ 12h, obtains a kind of magnalium hydrotalcite presoma MgAl-LDH；
Step 2: by SnCl2·2H2O is dissolved in deionized water, and holding continuously stirs 30 ~ 60min, forms 0.01 ~ 0.06mol/ The SnCl of L2Salting liquid, then ammonia precipitation process agent is added into gained salting liquid, stirring regulates and controls salting liquid pH=10 ± 0.5 to get arriving A kind of SnCl2·2H2O is hydrolyzed into SnO2White colloidal suspension；
Contain SnO made from second step step 3: magnalium hydrotalcite presoma made from the first step is added2White colloidal suspend In liquid, formed 30 ~ 65g/L of concentration, pH=10 ± 0.5 mixed solution, wherein Mg, Al, Sn molar ratio be 2.5 ~ 3.5:1:0.1 ~ 0.15,20 ~ 40 DEG C of 8 ~ 12h of mixing of room temperature obtain white depositions, centrifuge separation, ethanol washing white depositions, filter cake Dry 8 ~ 12h in 50 ~ 60 DEG C of insulating boxs, then be placed in box Muffle furnace and be warming up to 400 from room temperature with 1 ~ 3 DEG C/min heating rate ~ 600 DEG C of 3 ~ 6h of roasting, gained white solid powder is the solid base SnO after cooling2(Ⅱ)/MgAl-LDO。
By SnO described in 12(II)/MgAl-LDO catalyzed by solid base 5 hydroxymethyl furfural and acetone aldol reaction close It is by 5 hydroxymethyl furfural, acetone, SnO at the method for HAC ((E)-4- (5- methylol-2- furyl)-3- butene-2 -one)2 (II)/MgAl-LDO solid base is uniformly mixed according to the mass ratio of 1:4.2 ~ 4.8:0.04 ~ 0.06, is heated to 80 DEG C ~ 100 DEG C, It being stirred to react 2 ~ 3h, stops reaction, be cooled to room temperature, filter, filter cake washs 3 times with 20 ~ 40min of tetrahydrofuran ultrasound, and 50 ~ 70 DEG C after vacuum drying 8 ~ 12 hours, reuses standby next time as catalyst, obtained after filtration catalytic agent is extracted with ethyl acetate Liquid product, taking extract liquor upper layer glassy yellow oil reservoir is product (E)-4- (5- methylol-2- furyl)-3- butene-2- Ketone, 5 hydroxymethyl furfural conversion ratio is up to 99.84%, and for target product HAC selectivity up to 98.6%, target product HAC yield can Up to 98.76%, lower layer is the by-product and extractant ethyl acetate that the complete acetone of part unreacted and acetone self condense, and acetone is certainly Condensation product is that diacetone alcohol boiling point is 166 DEG C, 77 DEG C of ethyl acetate boiling point, 56 DEG C of acetone boiling point, by way of vacuum distillation Successively three is separated and recovered.
Advantage characteristic and technical effect of the present invention
1. combining hydrotalcite induced hydrolysis and heat treatment hydration method again, the SnO with hydrotalcite structure is synthesized2 (Ⅱ)/ MgAl layered di-hydroxyl composite metal oxidate, the hydroxy functional group and metal cation being distributed on laminate make neatly slabstone layer Structure is positively charged, SnO2It is combined with the oxygen-containing functional group-OH on magnalium hydrotalcite surface, to preferably be fixed on magnalium water In steatite support level, enhance alkali density and base strength.
2. stannous chloride is used to prepare SnO for tin source2 (II)/MgAl-LDO solid base, preparation cost is low, catalytic activity Height, stability is good, reusable.
3. SnO2 (II)/MgAl-LDO catalyzed by solid base is in the condensation reaction of 5 hydroxymethyl furfural and acetone, reaction temperature It is moderate, the reaction time is short, by-product is few, 100 DEG C, reaction 2 hours, 5 hydroxymethyl furfural conversion ratio 99.83%, HAC yield 98.76%, acetone self condenses by-product yield less than 1%.
Detailed description of the invention
Scheme (1), (a) be the magnalium hydrotalcite presoma MgAl-LDH not roasted, and (b), (c), (d), (e), (f) is not The SnCl of the different quality content of roasting2·2H2The SnO that O is hydrolyzed to form2Composite magnesium aluminate hydrotalcite SnO2 (II)/MgAl-LDH XRD map.Scheme (1), in (a), (003), (006), (012), (015), (018), (110), (113) are hydrotalcite precursor The characteristic diffraction peak of MgAl-LDH.Scheme (1), (b), (c), (d), (e), (f), with load SnCl2·2H2O mass it is continuous Increase, still keeps hydrotalcite layered structure, the crystal faces such as (110), (113) are still clearly present, and show successfully to synthesize with water The SnO of talc lamellar structure2/MgAl-LDH.Occur slightly in 2 θ=26.5 ° (110) and 51.76 ° of (211) two approximate angle Wider and faint characteristic diffraction peak type is typical non crystalline structure feature, the peak position and JCPDS standard diffraction figure at the two peaks Card (card number: 21-1250) matches, and shows SnO2Particle is amorphous and size is very small, after 450 DEG C of roastings SnO2Crystal form is obvious, and SnO synthesized after gained roasts is calculated according to Scherrer formula2Particle crystallite dimension is 8 ~ 16nm.
Figure (2) (a) be roasting after magnalium hydrotalcite MgAl-LDO infared spectrum, scheme (2) (b), (c), (d), (e), (f) is the SnO after the different stannic oxide mass content roastings of load2(II)/MgAl-LDO infared spectrum.It is obvious in figure Find out SnO2(II)/MgAl-LDO has infrared spectrum similar with hydrotalcite MgAl-LDO.3442cm-1Broad peak is magnalium neatly The stretching vibration peak of hydroxyl and interlayer hydrone between stone veneer, 1647 cm-1The peak nearby occurred is the flexible vibration of crystalline water molecules It is dynamic, 1371 cm-1The peak at place is CO3 2-Stretching vibration.1000 cm can be significantly seen in figure-1Lower wave number section below Its corresponding lattice vibration for being M-O (M Mg, Al, Sn) of absorption peak and the bending of M-O-M and O-M-M shake, 662 cm-1 The peak at place belongs to the vibration peak of Sn-O-Sn, illustrates SnO2It successfully loads on MgAl neatly stone veneer.
Figure (3) is that 15%(molecule is SnCl2·2H2O mass, denominator are carrier MgAl-LDH mass, similarly hereinafter) SnO2/ The CO of MgAl-LDO2- TPD measurement.Find out from figure (3), due to catalyst alkalescent site and CO2Interaction so that 100 ~ 200 DEG C of sections show there is a small amount of alkalescent site in catalyst surface nearby with the presence of weak parsing peak.300~450℃ Corresponding CO2Desorption peaks can corresponding be moderate strength basic site, belong to strong basicity within the temperature range of 500 ~ 600 DEG C Center.Catalyst there are it is weak, in strong three kinds of basic sites, three kinds of basic activated centers are desorbed peak areas: alkalescent site < in it is strong Basic site < strong basicity site.15%SnO2/ MgAl-LDO contain in, very alkaline active activated centre catalysis furfural acetone There is good catalytic effect on aldol reaction.
Scheming (4) is magnalium hydrotalcite MgAl-LDH (A), the 15%SnO not roasted2/ MgAl-LDH (B) and roasting after 15% SnO2/ MgAl-LDO (C)-(D) SEM figure, the scan position that (C), (D) two figure are chosen are different.From figure (4) (A) as it can be seen that The hexangle type magnalium hydrotalcite that the magnalium hydrotalcite MgAl-LDH pattern prepared under 120 DEG C of hydrothermal conditions tends to be more regular is brilliant Body.From the visible load SnO of figure (4) (B)215%SnO afterwards2No change has taken place for the pattern of/MgAl-LDH hydrotalcite, also not bright It is aobvious to see the SnO being dispersed on neatly stone veneer2.The 15%SnO after 450 DEG C of roastings is found out from figure (4) (C)-(D)2/ MgAl-LDH still keeps its laminated structure, and is dispersed with SnO on neatly stone veneer after roasting2In the presence of showing SnO2/MgAl- LDO has high thermal stability.
Specific embodiment
Embodiment 1
Step 1: nine nitric hydrate magnesium and six water aluminum nitrates are added simultaneously according to the ratio of Mg, Al molar ratio 3:1 at room temperature In deionized water, forming concentration in 35 DEG C of stirring and dissolvings is 0.53mol/L nitric acid magnalium mixing salt solution, the magnesium nitrate that will be obtained The sodium hydroxide solution of aluminium mixing salt solution and 1mol/L are slowly added into reactor simultaneously, control mixed solution in reactor 30min is stirred in pH=10, obtains white solid precipitating, gained mixture is transferred to the stainless steel hydro-thermal of polytetrafluoroethyllining lining In kettle, it is aged at 120 DEG C for 24 hours, with deionized water filtering and washing to neutrality, filtering by filter cake in 100 DEG C of dry 12h, that is, is made Obtain a kind of magnalium hydrotalcite presoma MgAl-LDH.
Step 2: taking the SnCl of certain mass2·2H2O is dissolved in deionized water, stirs 30min, forms 0.033mol/L SnCl2Salting liquid, then ammonia precipitation process agent is added into gained salting liquid, stirring regulation salting liquid pH=10 are a kind of to get arriving SnCl2·2H2O is hydrolyzed into SnO2White colloidal suspension.
Contain SnO made from second step step 3: magnalium hydrotalcite presoma made from the first step is added2White colloidal In suspension, the mixed solution of pH=10, concentration 57.5g/L is formed, 35 DEG C of mixing 8h obtain white depositions, are centrifuged It separates, ethanol washing white depositions, dry 12h in 60 DEG C of insulating boxs of filter cake, then is placed in box Muffle furnace from room temperature with 2 DEG C/min heating rate is warming up to 450 DEG C of roasting 4h, it is cooling after gained white solid powder be the solid base SnO2 (Ⅱ)/ MgAl-LDO, wherein Mg, Al, Sn molar ratio 3:1:0.13.
Step 4: by 1g 5 hydroxymethyl furfural, 4.6g acetone and 0.5g SnO2/ MgAl-LDO solid base magnetic agitation is mixed It closes uniformly, is heated to 100 DEG C, is stirred to react 2h, is cooled to room temperature after reaction, filter, filter cake tetrahydrofuran ultrasound 30min is washed 3 times, after 60 DEG C are dried in vacuo 12 hours, reuse standby next time as catalyst, filtering is extracted with ethyl acetate The liquid product obtained after catalyst, taking extract liquor upper layer glassy yellow oil reservoir is product HAC ((E) -4- (5- methylol -2- furan Mutter base)-3- butene-2 -one), 5 hydroxymethyl furfural conversion ratio is up to 99.83%, HAC product yield 98.60%, selectivity 98.76%, lower layer is the by-product and extractant ethyl acetate that the complete acetone of part unreacted and acetone self condense, acetone self shrinking It is 166 DEG C, 77 DEG C of ethyl acetate boiling point, 56 DEG C of acetone boiling point that close product, which be diacetone alcohol boiling point, by way of vacuum distillation according to It is secondary to separate and recover three.
Embodiment 2(comparative example) operating procedure is with embodiment 1, but reaction temperature is 110 DEG C, obtains 5 hydroxymethyl furfural furfural Conversion ratio 82.69%, HAC yield 75.21%, selectivity 90.95%.
3 operating procedure of embodiment is with embodiment 1, but reaction temperature is 90 DEG C, obtains 5 hydroxymethyl furfural furfural conversion ratio 97.55%, HAC yield 91.44%, selectivity 93.74%.
Embodiment 4(comparative example) operating procedure is with embodiment 1, but reaction temperature is 80 DEG C, obtains 5 hydroxymethyl furfural furfural Conversion ratio 96.73%, HAC yield 88.76%, selectivity 91.80%.
Embodiment 5(comparative example) operating procedure is with embodiment 1, but reaction temperature is 70 DEG C, obtains 5 hydroxymethyl furfural furfural Conversion ratio 86.63%, HAC yield are 67.80%, and selectivity is 78.3%.
Embodiment 6(comparative example) operating procedure is with embodiment 1, but the reaction time is 1h, and it obtains 5 hydroxymethyl furfural furfural and turns Rate 50.21%, HAC yield are 30.0%, and selectivity is 59.8%.
Embodiment 7(comparative example) operating procedure is with embodiment 1, but the reaction time is 3h, and it obtains 5 hydroxymethyl furfural furfural and turns Rate 99.62%, HAC yield are 86.89%, and selectivity is 87.22%.
Embodiment 8(comparative example) operating procedure is with embodiment 1, but 5 hydroxymethyl furfural and acetone quality ratio are 1:2.3, are obtained 5 hydroxymethyl furfural furfural conversion ratio 99.01%, HAC yield are 80.92%, and selectivity is 81.73%.
Embodiment 9(comparative example) operating procedure is with embodiment 1, but 5 hydroxymethyl furfural and acetone quality ratio are 1:6.9, are obtained 5 hydroxymethyl furfural furfural conversion ratio 99.13%, HAC yield are 78.20%, and selectivity is 79%.
11 operating procedure of embodiment is with embodiment 1, but SnO2/ MgAl-LDO catalyst amount is 0.6g, obtains 5- methylol Furfural furfural conversion ratio 99.65%, HAC yield 90.20%, selectivity 90.52%.
Embodiment 12(comparative example) operating procedure is with embodiment 1, but catalyst amount is 1g, obtains 5 hydroxymethyl furfural furfural Conversion ratio 99.03%, HAC yield are 59.0%, and selectivity is 60.0%.
Case study on implementation 13(comparative example) operating procedure with embodiment 1, changes SnCl2·2H2O load capacity, so that in catalyst Mg, Al, Sn molar ratio are 3:1:0.09, obtain 5 hydroxymethyl furfural furfural conversion ratio 96.00%, HAC yield 50.0%, selectivity 52.10%。
Case study on implementation 14(comparative example) operating procedure with embodiment 1, changes SnCl2·2H2O load capacity, so that in catalyst Mg, Al, Sn molar ratio are 3:1:0.18, obtain 5 hydroxymethyl furfural furfural conversion ratio 81.56%, and HAC yield is 47.0%, selection Property is 58.0%.
Case study on implementation 15(comparative example) operating procedure with embodiment 1, changes SnCl2·2H2O load capacity, so that in catalyst Mg, Al, Sn molar ratio are 3:1:0.22, obtain 5 hydroxymethyl furfural furfural conversion ratio 77.78%, and HAC yield is 42.0%, selection Property is 54.0%.
1 embodiment of table, 1~15 operating condition and reaction result

Claims (3)

1. a kind of SnO2(II)/MgAl-LDO solid base, it is characterized in that:
(1) SnO described in2(II) Mg, Al, Sn molar ratio 2.5 ~ 3.5:1:0.1 ~ 0.15 in/MgAl-LDO solid base；
(2) SnO described in2(II) in/MgAl-LDO solid base, SnO2It is dispersed in the hexagonal plate magnalium hydrotalcite of regular appearance On laminate, the SnO on neatly stone veneer is exposed to the open air2Nano microcrystalline is active site, in catalysis 5 hydroxymethyl furfural and acetone hydroxyl Aldehyde condensation reaction synthesis target product Aviation Fuel intermediate (E)-4- (5- methylol-2- furyl)-3- butene-2 -one (with Lower abbreviation HAC) in, acetone can be activated to lose α-H-shaped into nucleophilic carbanion intermediate well, then with another molecule 5- hydroxyl first Carbonyl carbon on base furfural carries out nucleophilic addition, forms new unsaturated carbon-carbon bond, obtains β-hydroxyl containing active α-H Base ketone, the beta-hydroxy ketone containing active α-H lose α, the beta unsaturated ketone that a molecular water forms more stable conjugated double bond structures again That is target product HAC, so that the SnO2(II)/MgAl-LDO solid base has high catalytic activity；
(3) SnO described in2(II)/MgAl-LDO solid base have hydrotalcite layered structure, 50 ~ 150nm of partial size, pore volume 0.2 ~ 0.9 cm3/ g, 30 ~ 130 m of specific surface area2/ g, basicity pKa=9 ~ 11.5 have 100 ~ 200 DEG C, 300 ~ 450 DEG C, 480 ~ 600 Three kinds of basic sites of weak, medium, strong in DEG C three different temperatures sections, SnO2Lacking oxygen and oxygen migration ability make it is described SnO2(II)/MgAl-LDO solid base catalyst has more low coordination oxygen, makes in catalyst, strong base concentrations all increased, Compared with simple magnalium hydrotalcite, increase specific surface area and in, strong basicity site, in catalysis 5 hydroxymethyl furfural and acetone Aldol reaction synthesizes in target product HAC, promotes the shape of the α-H carbanion intermediate and beta-hydroxy ketone on acetone At, while the presence in strong basicity site is more advantageous to intermediate C9Alcohol sloughs 1 hydrone water and forms target product HAC, so that institute The SnO stated2(II)/MgAl-LDO solid base catalyst has high selectivity.
2. preparing SnO as described in claim 12(II)/MgAl-LDO solid base method, it is characterized in that: being different from existing total Precipitating is that element proportion (Mg+Sn)/Al=2.8 ~ 3.2:1 or Mg/ (Sn+Al)=2.8 ~ 3.2:1 prepares tin same order elements part magnesium Or aluminum is for the method for SnMgAl-LDH, but hydrotalcite induced hydrolysis and heat treatment hydration method again are combined, with SnCl2· 2H2O is tin source, ammonium hydroxide is precipitating reagent, under salt-alkali environment of pH value 10 ± 0.5, so that SnCl2·2H2The SnO that O is hydrolyzed into2 By being combined with hydrotalcite surface oxygen-containing functional group-OH, to preferably be fixed in magnalium hydrotalcite carrier level, then pass through 400 ~ 600 DEG C of roastings obtain the SnO2(II)/MgAl-LDO, such Al3+It is not with Al2O3Object mutually exists, but Al3+Portion Divide and occupies Mg in MgO lattice2+Position, and MgO structure is not destroyed, do not form MgAl spinelle or MgO and MgAl2O4Two-phase, The SnO with hydrotalcite structure is made2(II)/MgAl-LDO, the specific steps are as follows:
Step 1: at room temperature according to the ratio of 2.5 ~ 3.5:1 of Mg, Al molar ratio, nine nitric hydrate magnesium and six water aluminum nitrates are same When be added in deionized water, forming concentration in 25 ~ 37 DEG C of stirring and dissolvings is that 0.48 ~ 0.55mol/L nitric acid magnalium salt-mixture is molten Liquid by the sodium hydroxide solution of obtained nitric acid magnalium mixing salt solution and 0.8 ~ 1.2mol/L while being slowly added into reactor In, mixed solution pH=10 ± 0.5 in reactor is controlled, 30 ~ 60min is stirred, white solid precipitating is obtained, by gained mixture Be transferred in the stainless steel water heating kettle of polytetrafluoroethyllining lining, 100 ~ 120 DEG C be aged 18 ~ for 24 hours, with deionized water filtering and washing To neutrality, filtering by filter cake in 100 ~ 120 DEG C of dry 8 ~ 12h, obtains a kind of magnalium hydrotalcite presoma MgAl-LDH；
Step 2: by SnCl2·2H2O is dissolved in deionized water, and holding continuously stirs 30 ~ 60min, forms 0.01 ~ 0.06mol/L SnCl2Salting liquid, then ammonia precipitation process agent is added into gained salting liquid, stirring regulates and controls salting liquid pH=10 ± 0.5 to get arriving A kind of SnCl2·2H2O is hydrolyzed into SnO2White colloidal suspension；
Contain SnO made from second step step 3: magnalium hydrotalcite presoma made from the first step is added2White colloidal suspend In liquid, formed 30 ~ 65g/L of concentration, pH=10 ± 0.5 mixed solution, wherein Mg, Al, Sn molar ratio be 2.5 ~ 3.5:1:0.1 ~ 0.15,20 ~ 40 DEG C of 8 ~ 12h of mixing of room temperature obtain white depositions, centrifuge separation, ethanol washing white depositions, filter cake Dry 8 ~ 12h in 50 ~ 60 DEG C of insulating boxs, then be placed in box Muffle furnace and be warming up to 400 from room temperature with 1 ~ 3 DEG C/min heating rate ~ 600 DEG C of 3 ~ 6h of roasting, gained white solid powder is the solid base SnO after cooling2(Ⅱ)/MgAl-LDO。
3. by SnO described in claim 12(II)/MgAl-LDO catalyzed by solid base 5 hydroxymethyl furfural and acetone aldol condensation are anti- The method that HAC ((E)-4- (5- methylol-2- furyl)-3- butene-2 -one) should be synthesized, it is characterized in that: by 5- methylol chaff Aldehyde, acetone, SnO2(II)/MgAl-LDO solid base is uniformly mixed according to the mass ratio of 1:4.2 ~ 4.8:0.4 ~ 0.8, is heated to 80 DEG C ~ 100 DEG C, it is stirred to react 2 ~ 3h, stops reaction, is cooled to room temperature, is filtered, filter cake is washed with 20 ~ 40min of tetrahydrofuran ultrasound It 3 times, after 50 ~ 70 DEG C are dried in vacuo 8 ~ 12 hours, are reused standby next time as catalyst, filtration catalytic is extracted with ethyl acetate The liquid product obtained after agent, taking extract liquor upper layer glassy yellow oil reservoir is product (E) -4- (5- methylol -2- furyl) -3- Butene-2 -one, 5 hydroxymethyl furfural conversion ratio is up to 99.84%, and target product HAC selectivity is up to 98.6%, target product For HAC yield up to 98.76%, lower layer is the by-product that the complete acetone of part unreacted and acetone self condense and extractant acetic acid second Ester, it is 166 DEG C, 77 DEG C of ethyl acetate boiling point, 56 DEG C of acetone boiling point that it is diacetone alcohol boiling point that acetone, which self condenses product, passes through decompression Distillation mode successively separates and recovers three.
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CN110586079A (en) * 2019-09-23 2019-12-20 湘潭大学 Preparation and application of layered CaMnAl hydrotalcite solid base catalyst
CN111484395A (en) * 2020-05-20 2020-08-04 青岛科技大学 Method for recovering bisphenol A by catalyzing polycarbonate to carry out methanol alcoholysis by composite metal oxide
CN112495360A (en) * 2020-11-23 2021-03-16 浙江恒澜科技有限公司 Solid composite catalyst for continuously preparing 3-hydroxybutyraldehyde, and preparation method and application thereof
CN115709073A (en) * 2022-10-17 2023-02-24 山东农业大学 Preparation method of tin-based catalyst and application of tin-based catalyst in preparation of methyl lactate by catalyzing biomass sugar

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CN104148059A (en) * 2014-06-19 2014-11-19 北京化工大学 Reforming catalyst with high dispersion stability and preparation method thereof

Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN110586079A (en) * 2019-09-23 2019-12-20 湘潭大学 Preparation and application of layered CaMnAl hydrotalcite solid base catalyst
CN111484395A (en) * 2020-05-20 2020-08-04 青岛科技大学 Method for recovering bisphenol A by catalyzing polycarbonate to carry out methanol alcoholysis by composite metal oxide
CN111484395B (en) * 2020-05-20 2022-08-19 青岛科技大学 Method for recovering bisphenol A by catalyzing polycarbonate to carry out methanol alcoholysis by composite metal oxide
CN112495360A (en) * 2020-11-23 2021-03-16 浙江恒澜科技有限公司 Solid composite catalyst for continuously preparing 3-hydroxybutyraldehyde, and preparation method and application thereof
CN112495360B (en) * 2020-11-23 2022-07-08 浙江恒逸石化研究院有限公司 Solid composite catalyst for continuously preparing 3-hydroxybutyraldehyde, and preparation method and application thereof
CN115709073A (en) * 2022-10-17 2023-02-24 山东农业大学 Preparation method of tin-based catalyst and application of tin-based catalyst in preparation of methyl lactate by catalyzing biomass sugar
CN115709073B (en) * 2022-10-17 2024-04-26 山东农业大学 Preparation method of tin-based catalyst and application of tin-based catalyst in catalyzing biomass sugar to prepare methyl lactate

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