CN101274289A - Selective oxidation catalyst with environmental friendly supermolecular structure and method of preparing the same - Google Patents

Abstract

The invention discloses an environment-friendly and selective oxidation catalyst with super-molecular structure and a preparation method thereof, belonging to the technical field of catalyst synthesis. The oxidation catalyst has molecular composition of (M<2+>(1-x)M<3+>x(OH)2)<x+>(Ti(OH<->)b(CO3<2->)cOd)a(CO3<2->)e-mH2O and the following preparation steps: a houghite precursor that takes NO3<-> as the inter-laminar anions and 2 to 4 as the mol ratio M<2+>/M<3+> of the diatomic cations to the trivalent cations of laminar boards is prepared; metal Ti powder is processed with oxydol below 25 DEG C, the mol ratio of Ti to H2O2 is 1: 88, the reaction is implemented under agitation, and the agitation lasts for 8 to 12 hours, thus obtaining settled solution of yellow pertitanate composition; the obtained solution of pertitanate composition and the houghite precursor with the inter-laminar anions of NO3<-> are agitated for reaction at the temperature of 10 to 25 DEG C, and reaction products are completely washed by the water with CO2 removed, centrifuged and vacuum dried to obtain the selective oxidation catalyst with the super-molecular structure of the intercalated pertitanate composition and the houghite. The environment-friendly and selective oxidation catalyst with the super-molecular structure has the advantages of good selectivity and reusability.

Description

A kind of selective oxidation catalyst with environmental friendly supermolecular structure and preparation method thereof

Affiliated field

The invention belongs to the catalyst synthesis technical field, a kind of selective oxidation catalyst with environmental friendly supermolecular structure and preparation method thereof particularly is provided.

Background technology

Sulfide compound is extensively to be present in main organic sulfur compound in the oil products such as gasoline, diesel oil, and the burning back generates SO _xCause forming acid rain, cause environmental pollution and the infringement of human health, SO _xTo vehicle exhaust NO, CO, particularly NO _xAnd the discharging of particle (PM) has obvious facilitation, and the noble metal catalyst in the vehicle exhaust converter is poisoned, and causes the increase of pollutant effulent, SO _xAlso can corrode engine, reduce the life-span of engine.Therefore in view of the harm of sulfur-containing compound in the distillate, strict regulation is all made to the sulfur content in the distillate in countries in the world and area.This makes traditional hydrodesulfurization (HDS) technology be faced with great challenge.Realize the ultra-deep desulfurization hydrogenation reaction pressure should＜4.0MPa, temperature about 320 ℃～370 ℃, high-pressure process even require pressure to reach 10MPa, and use the catalyst of super-active.Though traditional diesel hydrogenation for removal sulphur technology can satisfy the quality requirement of straight-run diesel oil desulfurization,, the hydrogenation plant investment is big, and the operating cost height causes the diesel oil cost significantly to rise.Therefore people turn to more eyes on the non-hydrodesulfurization Study on Technology.Wherein, the tool potentiality of deep oxidation desulfurization.Compare with traditional hydrodesulfurization technology, oxidative desulfurization techniques has the following advantages: can remove thiophene and thioether that hydrogenation method is difficult for removing rapidly, i.e. and deep desulfuration, the reaction condition gentleness, atmospheric operation, technological process is simple, and equipment investment is extremely low, energy-conservation, low CO ₂The environment-protective process of discharging.Therefore oxidizing process is called as green desulfurization technology geared to the 21st century, is a up-and-coming desulfur technology.

In addition, the sulfide compound oxidation is divided into two stages, and the phase I sulfide oxidation generates sulfoxide, and the second stage sulfoxide continues oxidation and generates sulfone.Sulfide oxidation product sulfoxide and sulfone are again the important intermediate of organic syntheses such as fine chemistry industry, medicine, agricultural chemicals, have purposes widely.Sulfoxide is the emerging extractant of a class that grows up the sixties in 20th century, contains semi-polar S=O group in the sulfoxide molecule, and this group can generate co-ordination complex or solvate with metal ion effectively.Therefore sulfoxide can extract noble metals such as gold, silver, platinum in hydrochloric acid, sulfuric acid medium, also can extract rare earth elements such as uranium, thorium.More valuable is it can be from sodium tungstate solution selective extraction aluminium, reach the purpose of deep purifying sodium tungstate solution.Because sulfoxide has nontoxic odorless, the source is abundant simultaneously, low price, and to noble metal extraction yield height, good selective is subjected to domestic and international scientific worker's attention.And contain sulfone compound because of having broad-spectrum biological activity, as desinsection, sterilization, weeding, antitumor, antiviral etc., cause the concern of people to it, especially sulfuryl group is incorporated in the various compound structure, can produces a series of compound Chang Zuowei medicine or agricultural chemicals with broad-spectrum biological activity by structural modification.In having the agricultural biological activity compound, sulfone derivatives shows very big using value with various biologically actives such as its good desinsection, sterilization, weeding, plant growth regulating on agricultural.

In recent years owing to synthesized the transition metal complex catalyst of many novel, high activities and high selectivity, make many selectivity catalytic reactions reach very high selectivity and conversion ratio, thereby the huge power and the wide prospect of having showed selective oxidation organic synthesis method, yet the homogeneous complex catalyst has easy loss, difficult separation and recycling, complicated operation, is unsuitable for shortcomings such as continuous operation.Therefore, find suitable material to come the catalysis organic synthesis just to become the focus of numerous chemist's researchs as the carrier of transition metal complex.

The bimetallic complex hydroxide is called hydrotalcite (Layered Double Hydroxides again, be abbreviated as LDHs) be a kind of novel multifunctional stratified material, LDHs is because of having unique The Nomenclature Composition and Structure of Complexes characteristic, its chemical stability is good, is used widely in catalytic reaction thereby can be used as base catalyst, oxidation reduction catalyst, soda acid bifunctional catalyst and catalyst carrier etc.Insertion has the metal complex of catalytic performance and introduces the LDHs interlayer, and interlamellar spacing is increased, and reactant molecule can enter into the particular chemical environment of interlayer passage, has both improved the catalytic activity of material, helps again optionally to improve simultaneously.Pillared material with supramolecular structure can be applied even more extensively in more reaction system.

People are constantly finding in the research process, the transition metal titanium elements has the lower d track of energy, in the process that forms compound, demonstrate various spatial configurations, is the very promising catalyst for selective oxidation of a class with Ti (IV) for central metal ion titanium complex, has shown good catalytic activity and high selectivity in many reactions.Titanium can with multiple Atomic coordinate, when entering its coordination sphere, part shows distinctive coordination behavior, thereby, be that the catalyst of central ion is used widely in the selectivity catalytic reaction with the titanium, as epoxidation Reaction of Alkenes, thioether selective oxidation reaction etc.

Summary of the invention

The object of the invention is to provide a kind of selective oxidation catalyst with environmental friendly supermolecular structure and preparation method thereof, utilize the controlled and veneer structure orientation effect of interlayer ion interchangeability, laminate of LDHs, the pertitanic acid complex is introduced interlayer with anionic form, simultaneously can pass through modulation main body hydrotalcite grain size, modulation hydrotalcite laminate bivalent metal ion kind obtains the catalyst for selective oxidation with various grain sizes of different precursor intercalations.This catalyst is applied to the oxidation reaction of thioether, shows good selectivity and reusability.

Consisting of of supramolecular structure catalyst for selective oxidation of the present invention: with the interlayer anion is NO ₃ ^-Hydrotalcite be precursor, this hydrotalcite precursor has the composition that is shown below: [M ²⁺ _1-xM ³⁺ _x(OH) ₂] ^X+NO ₃ ^- _xMH ₂O, wherein, M ²⁺The expression divalent metal is selected from Mg ²⁺, Ni ²⁺, Co ²⁺, Zn ²⁺, Fe ²⁺And Cu ²⁺In one or more; M ³⁺The expression trivalent metal cation is selected from Al ³⁺, Cr ³⁺, Fe ³⁺, Ga ³⁺, In ³⁺In one or more, be preferably Al ³⁺ M represents the quantity of the crystallization water, 0.1≤m≤0.8; 0.2≤x≤0.33 replaces NO with pertitanic acid complex anion through ion-exchange ₃ ^-Enter hydrotalcite layers, constitute the anion pillared supermolecule stratified material of pertitanic acid complex, wherein complex molecule plays the effect of supporting the hydrotalcite layers distance in the interlayer monolayer alignment.

Molecular composition [the M of this catalyst ²⁺ _1-xM ³⁺ _x(OH) ₂] ^X+[Ti (OH ^-) _b(CO ₃ ^2-) _cO _d] _a(CO ₃ ^2-) _eMH ₂O wherein, M ²⁺The expression divalent metal can be selected from Mg ²⁺, Ni ²⁺, Co ²⁺, Zn ²⁺, Fe ²⁺And Cu ²⁺In one or more, be preferably Mg ²⁺, Zn ²⁺And Ni ²⁺In one or more; Trivalent metal cation can be selected from Al ³⁺, Cr ³⁺, Fe ³⁺, Ga ³⁺, In ³⁺In one or more, be preferably Al ³⁺ M represents the quantity of the crystallization water, 0.1≤m≤0.8; 0.2≤x≤0.33; [Ti (OH ^-) _b(CO ₃ ^2-) _cO _d] form for peroxidating metatitanic acid complex, a represents Ti content in the peroxidating metatitanic acid, and a=x-2e wherein, b are the quantity with the hydroxyl of titanium coordination, b=0,1,2,3, optimum is 3, c is and the quantity 0,1 of titanium coordination carbonate that optimum is 0; D is the quantity 1,2 of residue coordination oxygen, and optimum is 2; The quantity of e interlayer coexisting ion carbonate, 0≤e≤x/2, optimum are 0.

The preparation process of supramolecular structure catalyst for selective oxidation of the present invention is as follows:

A. provide the hydrotalcite precursor, preparation laminate divalence, Tricationic mol ratio M ²⁺/ M ³⁺=2～4 hydrotalcite precursor;

B. with the hydrogen peroxide of 8.8mol/L according to mol ratio Ti: H ₂O ₂Be that 1: 88 pair of metal Ti powder is handled, react after 8～12 hours and filter that it is 4～9 that filtrate is transferred its pH value with ammoniacal liquor, preparing concentration is the electronegative peroxidating metatitanic acid complex of 0.005mol/L～0.03mol/L;

C. be NO with pertitanic acid complex and interlayer anion ₃ ^-Hydrotalcite at N ₂Protection is also stirred down, and 10～25 ℃ were reacted 8～24 hours down, and product spends CO ₂Water fully washs, centrifugal, can obtain pertitanic acid complex intercalated houghite after 10～25 ℃ of vacuum drying;

The preparation-obtained pertitanic acid complex of the present invention can stable existence between pH=4～9 in solution.

Hydrotalcite main body laminate of the present invention is selected divalent metal Mg ²⁺, Zn ²⁺, Ni ²⁺In any and trivalent metal cation Al ³⁺Combination.

Supramolecular structure catalyst for selective oxidation of the present invention is a stratified material, and interlamellar spacing is at 0.97～1.02nm.

In step c, the ratio of Ti content is 2: 1～7: 1 in hydrotalcite precursor laminate trivalent metal and the titanium complex solution.

The preparation method of described hydrotalcite precursor comprises:

A. provide the mixed solution that contains solubility divalent metal salt and solubility trivalent metal salt, bivalent metal ion M ²⁺With trivalent metal ion M ³⁺Mol ratio be 2～4;

B. provide the mixed solution that contains solubility divalent metal salt and solubility trivalent metal salt, bivalent metal ion M ²⁺With trivalent metal ion M ³⁺Mol ratio be 2,140 ℃ of static crystallization 24h obtain Mg in the reactor ₂Al-CO ₃The LDHs precursor.With Mg ₂Al-CO ₃LDHs joins the NaNO that is dissolved with 0.3mol ₃In the solution, NO ₃ ^-/ CO ₃ ^2-=30, the back adds the dense HNO of 0.001mol ₃, N ₂Crystallization 24h is stirred in protection under the room temperature, obtain the Mg of 1000～1400nm ₂Al-NO ₃LDHs, Mg ²⁺/ Al ³⁺=2.

Above-mentioned material is carried out XRD, IR, Raman, TG-MS, the success of elemental analysis demonstration titanium complex intercalation.The XRD structural parameters show that its laminate spacing increases greatly behind the titanium complex intercalation, and its cell parameter a value remains unchanged before and after intercalation, product has complete layer structure, and analyze with FT-IR and to show that all titanium complex inserts the LDHs interlayer, and perpendicular to the interlayer that is arranged in hydrotalcite.

The invention has the advantages that: but the controlled and veneer structure orientation effect of intercalation assembleability, laminate of hydrotalcite stratified material utilized, pertitanic acid complex intercalation with catalytic performance is entered hydrotalcite layers, realize the high degree of dispersion of pertitanic acid complex in hydrotalcite layers; Also but modulation laminate density metal and laminate metal species prepare the titanium complex interlayer inorganic supramolecular structure catalyst that is uniformly dispersed simultaneously, have improved the selectivity of product simultaneously.

The specific embodiment:

Embodiment 1

Steps A: take by weighing 0.06mol Mg (NO ₃) ₂6H ₂O and 0.03mol Al (NO ₃) ₃9H ₂O is dissolved in 100ml and removes CO ₂Water preparation mixing salt solution, other gets 0.18molNaOH and is dissolved in 100ml and removes CO ₂In the water, N under the room temperature ₂Protection is added drop-wise to aqueous slkali in the mixing salt solution of vigorous stirring, and control titration end-point pH is 10,100 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains Mg ₂Al-NO ₃LDHs, its Mg ²⁺/ Al ³⁺=2.

Step B: 0.5g metal Ti powder pressed powder added fill in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, the yellow clear filtrate of gained is the pertitanic acid complex solution.Regulate filtrate pH value with ammoniacal liquor and be 4, standby.

Step C:N ₂Under the protection, with 0.15g Mg ₂Al-NO ₃The LDHs adding fills 35ml and removes CO ₂In the reactor of deionized water, treat that solid all disperses the back to add 35ml titanium complex solution, normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of the peroxidating metatitanic acid complex of 30～40nm.

By X-ray diffractogram as can be known, titanium complex is after ion-exchange enters the LDHs interlayer, and its laminate spacing increases to 0.981nm by the 0.880nm of precursor; Two kinds of LDHs have the obvious diffraction peak near 2 θ are 61 °, and corresponding cell parameter a is approximately 0.304m, illustrate that titanium complex intercalation front and back LDHs laminate charge density does not change, and the LDHs laminate obtains more complete maintenance.The IR spectrogram shows, the Mg for preparing ₂Al-Ti LDHs is at 850cm ^-1, 670cm ^-1, 434cm ^-1The place occurred-characteristic peak of O-Ti-O; The Raman spectrogram is presented at 912cm ^-1, 682cm ^-1, 638cm ^-1, 397cm ^-1, 296cm ^-1, 152cm ^-1The success of proof Ti complex intercalation.

Embodiment 2

Steps A: take by weighing 0.06mol Mg (NO ₃) ₂6H ₂O and 0.03mol Al (NO ₃) ₃9H ₂O is dissolved in 100ml and removes CO ₂Water preparation mixing salt solution, other gets 0.18molNaOH and is dissolved in 100ml and removes CO ₂In the water, N under the room temperature ₂Protection is added drop-wise to aqueous slkali in the mixing salt solution of vigorous stirring, and control titration end-point pH is 10,100 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains Mg ₂Al-NO ₃LDHs, its Mg ²⁺/ Al ³⁺=2.

Step B: 0.5g metal Ti powder pressed powder added fill in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, the yellow clear filtrate of gained is the pertitanic acid complex solution.Regulate filtrate pH value with ammoniacal liquor and be 5, standby.

Step C:N ₂Under the protection, with 0.15g Mg ₂Al-NO ₃The LDHs adding fills 35ml and removes CO ₂In the reactor of deionized water, treat that solid all disperses the back to add 35ml titanium complex solution, normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of peroxidating metatitanic acid complex.

Embodiment 3

Steps A: take by weighing 0.06mol Mg (NO ₃) ₂6H ₂O and 0.03mol Al (NO ₃) ₃9H ₂O is dissolved in 100ml and removes CO ₂Water preparation mixing salt solution, other gets 0.18molNaOH and is dissolved in 100ml and removes CO ₂In the water, N under the room temperature ₂Protection is added drop-wise to aqueous slkali in the mixing salt solution of vigorous stirring, and control titration end-point pH is 10,100 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains Mg ₂Al-NO ₃LDHs, its Mg ²⁺/ Al ³⁺=2.

Step B: 0.5g metal Ti powder pressed powder added fill in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, the yellow clear filtrate of gained is the pertitanic acid complex solution.Regulate filtrate pH value with ammoniacal liquor and be 6, standby.

Step C:N ₂Under the protection, with 0.15g Mg ₂Al-NO ₃The LDHs adding fills 35ml and removes CO ₂In the reactor of deionized water, treat that solid all disperses the back to add 35ml titanium complex solution, normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of peroxidating metatitanic acid complex.

Embodiment 4

Steps A: take by weighing 0.06mol Mg (NO ₃) ₂6H ₂O and 0.03mol Al (NO ₃) ₃9H ₂O is dissolved in 100ml and removes CO ₂Water preparation mixing salt solution, other gets 0.18mol NaOH and is dissolved in 100ml and removes CO ₂In the water, N under the room temperature ₂Protection is added drop-wise to aqueous slkali in the mixing salt solution of vigorous stirring, and control titration end-point pH is 10,100 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains Mg ₂Al-NO ₃LDHs, its Mg ²⁺/ Al ³⁺=2.

Step B: 0.5g metal Ti powder pressed powder added fill in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, the yellow clear filtrate of gained is the pertitanic acid complex solution.Regulate filtrate pH value with ammoniacal liquor and be 7, standby.

Step C:N ₂Under the protection, with 0.15g Mg ₂Al-NO ₃The LDHs adding fills 35ml and removes CO ₂In the reactor of deionized water, treat that solid all disperses the back to add 35ml titanium complex solution, normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of peroxidating metatitanic acid complex.

Embodiment 5

Steps A: take by weighing 0.06mol Mg (NO ₃) ₂6H ₂O and 0.03mol Al (NO ₃) ₃9H ₂O is dissolved in 100ml and removes CO ₂Water preparation mixing salt solution, other gets 0.18mol NaOH and is dissolved in 100ml and removes CO ₂In the water, N under the room temperature ₂Protection is added drop-wise to aqueous slkali in the mixing salt solution of vigorous stirring, and control titration end-point pH is 10,100 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains Mg ₂Al-NO ₃LDHs, its Mg ²⁺/ Al ³⁺=2.

Step B: 0.5g metal Ti powder pressed powder added fill in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, the yellow clear filtrate of gained is the pertitanic acid complex solution.Regulate filtrate pH value with ammoniacal liquor and be 9, standby.

Step C:N ₂Under the protection, with 0.15g Mg ₂Al-NO ₃The LDHs adding fills 35ml and removes CO ₂In the reactor of deionized water, treat that solid all disperses the back to add 35ml titanium complex solution, normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of peroxidating metatitanic acid complex.

Embodiment 6

Steps A: take by weighing 0.06mol Mg (NO ₃) ₂6H ₂O and 0.03mol Al (NO ₃) ₃9H ₂O is dissolved in 100ml and removes CO ₂Water preparation mixing salt solution, other gets 0.18mol NaOH and is dissolved in 100ml and removes CO ₂In the water, N under the room temperature ₂Protection is added drop-wise to aqueous slkali in the mixing salt solution of vigorous stirring, and control titration end-point pH is 10,100 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains Mg ₂Al-NO ₃LDHs, its Mg ²⁺/ Al ³⁺=2.

Step B: 0.5g metal Ti powder pressed powder added fill in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, the yellow clear filtrate of gained is the pertitanic acid complex solution.Regulate filtrate pH value with ammoniacal liquor and be 7, standby.

Step C:N ₂Under the protection, with 0.15gMg ₂Al-NO ₃LDHs adds in the 35ml titanium complex solution, and normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of peroxidating metatitanic acid complex.

Embodiment 7

Steps A: take by weighing 0.06mol Mg (NO ₃) ₂6H ₂O and 0.03mol Al (NO ₃) ₃9H ₂O is dissolved in 100ml and removes CO ₂Water preparation mixing salt solution, other gets 0.18mol NaOH and is dissolved in 100ml and removes CO ₂In the water, N under the room temperature ₂Protection is added drop-wise to aqueous slkali in the mixing salt solution of vigorous stirring, and control titration end-point pH is 10,100 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains Mg ₂Al-NO ₃LDHs, its Mg ²⁺/ Al ³⁺=2.

Step B: 0.5g metal Ti powder pressed powder added fill in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, the yellow clear filtrate of gained is the pertitanic acid complex solution.Regulate filtrate pH value with ammoniacal liquor and be 7, standby.

Step C:N ₂Under the protection, with 0.15g Mg ₂Al-NO ₃The LDHs adding fills 70ml and removes CO ₂In the reactor of deionized water, treat that solid all disperses the back to add 35ml titanium complex solution, normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of peroxidating metatitanic acid complex.

Embodiment 8

Steps A: take by weighing 0.06mol Mg (NO ₃) ₂6H ₂O and 0.02mol Al (NO ₃) ₃9H ₂O is dissolved in 100ml and removes CO ₂Water preparation mixing salt solution, other gets 0.16mol NaOH and is dissolved in 100ml and removes CO ₂In the water, N under the room temperature ₂Protection is added drop-wise to aqueous slkali in the mixing salt solution of vigorous stirring, and control titration end-point pH is 10,100 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains Mg ₂Al-NO ₃LDHs, its Mg ²⁺/ Al ³⁺=3.

Step B: 0.5g metal Ti powder pressed powder added fill in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, the yellow clear filtrate of gained is the pertitanic acid complex solution.Regulate filtrate pH value with ammoniacal liquor and be 7, standby.

Step C:N ₂Under the protection, with 0.15gMg ₂Al-NO ₃The LDHs adding fills 35ml and removes CO ₂In the reactor of deionized water, treat that solid all disperses the back to add 35ml titanium complex solution, normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of peroxidating metatitanic acid complex.

Embodiment 9

Steps A: take by weighing 0.06mol Mg (NO ₃) ₂6H ₂O and 0.015mol Al (NO ₃) ₃9H ₂O is dissolved in 100ml and removes CO ₂Water preparation mixing salt solution, other gets 0.15mol NaOH and is dissolved in 100ml and removes CO ₂In the water, N under the room temperature ₂Protection is added drop-wise to aqueous slkali in the mixing salt solution of vigorous stirring, and control titration end-point pH is 10,100 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains Mg ₂Al-NO ₃LDHs, its Mg ²⁺/ Al ³⁺=4.

Step B: 0.5g metal Ti powder pressed powder added fill in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, the yellow clear filtrate of gained is the pertitanic acid complex solution.Regulate filtrate pH value with ammoniacal liquor and be 7, standby.

Step C:N ₂Under the protection, with 0.15gMg ₂Al-NO ₃The LDHs adding fills 35ml and removes CO ₂In the reactor of deionized water, treat that solid all disperses the back to add 35ml titanium complex solution, normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of peroxidating metatitanic acid complex.

Embodiment 10

Steps A: take that the steps A method obtains Zn in the similar embodiment 1 ₂Al-NO ₃The LDHs precursor.Take by weighing 0.06molZn (NO ₃) ₂6H ₂O and 0.03mol Al (NO ₃) ₃9H ₂O is dissolved in 100ml and removes CO ₂Water preparation mixing salt solution, other gets 0.18molNaOH and is dissolved in 100ml and removes CO ₂In the water, N under the room temperature ₂Protection is added drop-wise to aqueous slkali in the mixing salt solution of vigorous stirring by given pace, control titration end-point pH is 8,100 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains Zn ₂Al-NO ₃LDHs, its Zn ²⁺/ Al ³⁺=1.3.

Step B: by the method for step B in the similar embodiment 1,0.5g metal Ti powder pressed powder added fill in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, and the yellow clear filtrate of gained is titanium complex solution.Regulate filtrate pH value with ammoniacal liquor and be 6～7, standby.

Step C: take step C method in the similar embodiment 1, N ₂Under the protection, with 0.18g Zn ₂Al-NO ₃The LDHs adding fills 35ml and removes CO ₂In the reactor of deionized water, treat that solid all disperses the back to add 35ml titanium complex solution, normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of peroxidating metatitanic acid complex.

By X-ray diffractogram as can be known, titanium complex is after ion-exchange enters the LDHs interlayer, and its laminate spacing increases to 1.00nm by the 0.892nm of precursor; Two kinds of LDHs have the obvious diffraction peak near 2 θ are 61 °, and corresponding cell parameter a is approximately 0.304nm, illustrate that titanium complex intercalation front and back LDHs laminate charge density does not change, and the LDHs laminate obtains more complete maintenance.The IR spectrogram shows, the Zn for preparing ₂Al-Ti LDHs is at 860cm ^-1, 778cm ^-1The place occurred-characteristic peak of O-Ti-O, prove that Ti complex intercalation is successfully.

Embodiment 11

Steps A: take that the steps A method obtains Ni in the similar embodiment 1 ₂Al-NO ₃The LDHs precursor.Take by weighing 0.06molNi (NO ₃) ₂6H ₂O and 0.03mol Al (NO ₃) ₃9H ₂O is dissolved in 100ml and removes CO ₂Water preparation mixing salt solution, other gets 0.18mol NaOH and is dissolved in 100ml and removes CO ₂In the water, N under the room temperature ₂Protection is added drop-wise to aqueous slkali in the mixing salt solution of vigorous stirring by given pace, control titration end-point pH is 6,100 ℃ of crystallization 24h of gained slurries, and the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains Ni ₂Al-NO ₃LDHs, its Ni ²⁺/ Al ³⁺=1.6.

Step B: by the method for step B in the similar embodiment 1,0.5g adding, metal Ti powder pressed powder fills in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, and the yellow clear filtrate of gained is titanium complex solution.Regulate filtrate pH value with ammoniacal liquor and be 7, standby.

Step C: take step C method in the similar embodiment 1, N ₂Under the protection, with 0.25g Ni ₂Al-NO ₃The LDHs adding fills 35ml and removes CO ₂In the reactor of deionized water, treat that solid all disperses the back to add 35ml titanium complex solution, normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of peroxidating metatitanic acid complex.

By X-ray diffractogram as can be known, titanium complex is after ion-exchange enters the LDHs interlayer, and its laminate spacing increases to 1.00nm by the 0.892nm of precursor; Two kinds of LDHs have the obvious diffraction peak near 2 θ are 61 °, and corresponding cell parameter a is approximately 0.304nm, illustrate that titanium complex intercalation front and back LDHs laminate charge density does not change, and the LDHs laminate obtains more complete maintenance.The IR spectrogram shows, the Ni for preparing ₂Al-Ti LDHs is at 850cm ^-1The place occurred-characteristic peak of O-Ti-O, prove that Ti complex intercalation is successfully.

Embodiment 12

Steps A: take by weighing 0.02mol Mg (NO ₃) ₂6H ₂O and 0.01mol Al (NO ₃) ₃9H ₂O is dissolved in 40ml and removes CO ₂Water mixed preparing salting liquid takes by weighing 0.026M C ₆H ₁₂N ₄Be dissolved in 40ml and remove CO ₂Water mixes two kinds of solution rapidly under stirring, transfers in the reactor, and 140 ℃ of static crystallization 24h, the product centrifuge washing is to neutral, and 80 ℃ of dryings obtain Mg ₂Al-CO ₃The LDHs precursor.

Step B: take by weighing 0.2g Mg ₂Al-CO ₃LDHs joins and is dissolved with 0.3mol NaNO ₃100ml remove CO ₂In the water, and add the dense HNO of 0.001mol ₃, N ₂Crystallization 24h is stirred in protection under the room temperature, the product centrifuge washing is to neutral; The gained sample characterizes behind the dry 24h down for 80 ℃, obtains the Mg of 1000-1400nm ₂Al-NO ₃LDHs, Mg ²⁺/ Al ³⁺=2.

Step C: add by the method 0.5g metal Ti powder pressed powder of step B among the embodiment 1 and to fill in the there-necked flask of hydrogen peroxide that 100ml concentration is 8.8mol/L, 0～25 ℃ of control reaction temperature, behind reaction 8～12h, reaction solution is filtered, the yellow clear filtrate of gained is titanium complex solution.Regulate filtrate pH value with ammoniacal liquor and be 7, standby.

Step D: take step C method in the similar embodiment 1, N ₂Under the protection, with 0.15g Mg ₂Al-NO ₃The LDHs adding fills 35ml and removes CO ₂In the reactor of deionized water, treat that solid all disperses the back to add 35ml titanium complex solution, normal temperature is reaction 8～24h down.Product spends CO ₂Water washing 3 times, vacuum drying 4h under the room temperature can obtain the stratified material of peroxidating metatitanic acid complex.

By X-ray diffractogram as can be known, titanium complex is after ion-exchange enters the LDHs interlayer, and its laminate spacing increases to 1.00nm by the 0.892nm of precursor; Two kinds of LDHs have the obvious diffraction peak near 2 θ are 61 °, and corresponding cell parameter a is approximately 0.304nm, illustrate that titanium complex intercalation front and back LDHs laminate charge density does not change, and the LDHs laminate obtains more complete maintenance.The IR spectrogram shows, the Mg for preparing ₂Al-Ti LDHs is at 782cm ^-1, 670cm ^-1, 451cm ^-1The place occurred-characteristic peak of O-Ti-O; The success of proof Ti complex intercalation.

Embodiment 13

With all titanium complex intercalated houghite super molecular compounds of making in embodiment 4,10,11 and 12 oxidation catalyst as the phenyl methyl thioether, under 313K, react, working concentration is the H of 8.8mol/L ₂O ₂Be oxidant, CH ₃CN is a solvent, phenyl methyl thioether/catalyst/H ₂O ₂Mol ratio be 1: 0.01～0.10: 2.Measure the 10ml solvent, add 117 μ l phenyl methyl thioethers, in the 313K shaking table, react, reaction 4-17h.The reaction solution that extracted 10 μ L every one hour from reaction system places test tube, adds 0.03g Na ₂SO ₃With excessive hydroperoxidation, add the acetone of 1ml, use the microfilter of 0.45 μ m to filter solid, the filter liquor conversion ratio and the chemo-selective of gas chromatograph-mass spectrometer detection reaction.Compare with titanium complex, the selectivity and the TON of titanium complex intercalated houghite all increase, and keep being better than the reusability of complex.

Claims (9)

1. supramolecular structure oxidation catalyst, the molecular composition [M of this catalyst ²⁺ _1-xM ³⁺ _x(OH) ₂] ^X+[Ti (OH ^-) _b(CO ₃ ^2-) _cO _d] _a(CO ₃ ^2-) _eMH ₂O, wherein, M ²⁺The expression divalent metal is selected from Mg ²⁺, Ni ²⁺, Co ²⁺, Zn ²⁺, Fe ²⁺And Cu ²⁺In one or more, M ³⁺The expression trivalent metal cation is selected from Al ³⁺, Cr ³⁺, Fe ³⁺, Ga ³⁺, In ³⁺In one or more; M represents the quantity of the crystallization water, 0.1≤m≤0.8; 0.2≤x≤0.33; [Ti (OH ^-) _b(CO ₃ ^2-) _cO _d] form for peroxidating metatitanic acid complex, a represents Ti content in the peroxidating metatitanic acid, wherein a=x-2e, b is the quantity with the hydroxyl of titanium coordination, b=0,1,2,3, c is the quantity with titanium coordination carbonate, the value of c is 0,1, and d is the quantity of residue coordination oxygen, the value of d is 1,2, the quantity of e interlayer coexisting ion carbonate, 0≤e≤x/2, the synthetic and design feature of this supramolecular structure catalyst for selective oxidation is: the pertitanic acid complex replaces NO ₃ ^-, enter hydrotalcite layers, constitute the pillared anionic supermolecule stratified material of metal complex, wherein complex molecule plays the effect of supporting the hydrotalcite layers distance in the interlayer monolayer alignment.

2. according to right 1 described supramolecular structure oxidation catalyst, it is characterized in that: M ²⁺Be Mg ²⁺, Zn ²⁺Or Ni ²⁺, M ³⁺Be Al ³⁺, M ²⁺With M ³⁺Ratio be 2: 1～4: 1.

3. according to right 1 described supramolecular structure oxidation catalyst, it is characterized in that: interlamellar spacing is in 0.97～1.00nm scope.

4. the preparation method of an environmentally friendly supramolecular structure oxidation catalyst, it is characterized in that: this method may further comprise the steps:

A., the hydrotalcite precursor is provided, and this hydrotalcite precursor has the composition that is shown below:

[M ²⁺ _1-xM ³⁺ _x(OH) ₂] ^x+NO ₃ ^- _x·mH ₂O，

Wherein, M ²⁺The expression divalent metal is selected from Mg ²⁺, Ni ²⁺, Co ²⁺, Zn ²⁺, Fe ²⁺And Cu ²⁺In one or more; M ³⁺The expression trivalent metal cation is selected from Al ³⁺, Cr ³⁺, Fe ³⁺, Ga ³⁺, In ³⁺In one or more; M represents the quantity of the crystallization water, 0.1≤m≤0.8; 0.2≤x≤0.33;

B. with the hydrogen peroxide of 8.8mol/L according to mol ratio Ti: H ₂O ₂Be that 1: 88 pair of metal Ti powder is handled, react after 8-12 hour and filter that it is 4～9 that filtrate is transferred its pH value with ammoniacal liquor, preparing concentration is the electronegative peroxidating metatitanic acid complex of 0.005mol/L～0.03mol/L;

C. the solution that makes among the hydrotalcite precursor that provides among the step a and the step b is mixed, titanium concentration is 0.007mol/L～0.02mol/L in the mixed solution, at N ₂Protection is also stirred down, and 10～25 ℃ were reacted 8～24 hours down, and product spends CO ₂Solid product is reclaimed in water washing, centrifugal, and 10～25 ℃ of vacuum drying obtain peroxidating metatitanic acid complex intercalated houghite.

5. method according to claim 4, wherein, in step b, the concentration of the peroxidating metatitanic acid complex that makes is 0.005mol/L～0.03mol/L.

6. method according to claim 4, wherein, in step b, the scope of the pH value of titanium complex solution is 4～9.

7. method according to claim 4, wherein, in step c, the ratio of Ti content is 2: 1～7: 1 in hydrotalcite precursor laminate trivalent metal and the titanium complex solution.

8. method according to claim 4, the preparation method of described hydrotalcite precursor comprises:

A. provide the mixed solution that contains solubility divalent metal salt and solubility trivalent metal salt, bivalent metal ion M ²⁺With trivalent metal ion M ³⁺Mol ratio be 2～4;

B. provide the mixed solution that contains solubility divalent metal salt and solubility trivalent metal salt, bivalent metal ion M ²⁺With trivalent metal ion M ³⁺Mol ratio be 2,140 ℃ of static crystallization 24h obtain Mg in the reactor ₂Al-CO ₃The LDHs precursor.With Mg ₂Al-CO ₃LDHs joins the NaNO that is dissolved with 0.3mol ₃In the solution, NO ₃ ^-/ CO ₃ ^2-=30, the back adds the dense HNO of 0.001mol ₃, N ₂Crystallization 24h is stirred in protection under the room temperature, obtain the Mg of 1000～1400nm ₂Al-NO ₃LDHs, Mg ²⁺/ Al ³⁺=2.

9. method according to claim 4, the grain size range of pertitanic acid hydrotalcite intercalation product is at 30～1400nm.