CN102274755B - Heterogeneous catalyst for synthesis of phenol, and preparation method and application thereof - Google Patents
Heterogeneous catalyst for synthesis of phenol, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a heterogeneous catalyst for the synthesis of phenol, and a preparation method and application thereof. The preparation method of the copper Schiff base/heteropoly acid supermolecular compound which is shown in formula (I) and loaded on a silicon-based molecular sieve comprises the functional group modification of a carrier, the preparation of a loaded copper Schiff base complex, the supermolecular combination of the copper complex loaded on the silicon-based molecular sieve and heteropoly acid and the like. In the formula (I), X3 is one of the following elements or groups: S, CONH-, OCO- and O. X1/X2 is one of the following elements or groups: F, Cl, Br, I, NO2, R, C(CH3)3, COOR, OR and H. Y is NHR or NR2. Z is one of the following groups: -CH2-(CH2)n-CH2-C6H10 and C6H4, wherein n is 0 or 1. POM is H3+nPW12-nVnO40 or H3+nPMo12-nVnO40, wherein n is 1-3. R is CH3, C2H5 or C3H7. The compound can be used in the synthesis reaction for directly oxidizing benzene into phenol.
Description
Technical field
The invention belongs to technical field of chemistry and chemical engineering, be specifically related to a kind of heterogeneous catalyst for the synthesis of phenol and its preparation method and application.
Background technology
Phenol is important industrial chemicals, is widely used in the production of the multiple macromolecule raw materials such as antiager, pharmaceutical intermediate and dihydroxyphenyl propane, resol, nylon-6.The production method that adopts at present is isopropyl benzene three step process method, and benzene and propylene generate first isopropyl benzene under the lewis acid catalysis, become hydrogen phosphide cumene through cumene oxidation again, decomposes to obtain phenol and acetone under effect of sulfuric acid again.The main drawback that this technique exists is that once through yield is low, needs to process a large amount of by product acetone, and explosive intermediate compound hydrogen phosphide cumene is unfavorable for safety in production.The benzene direct oxidation connects the phenol production approach that a hydroxyl synthesizing phenol provides a high atom utilization at phenyl ring.
Benzene direct oxidation synthesizing phenol can be divided into vapor phase process and liquid phase method, and vapor phase process generally is take HZSM-5, Fe/HZSM-5, TS-1 acid zeolite or carried noble metal as catalyzer, benzene vapor and N on fixed-bed reactor
2O, O
2At reducing gas such as H
2, the auxiliary lower direct reaction of CO generates phenol.Vapor phase process needs temperature high, and the as easy as rolling off a log by products such as quinone, diphenol that are oxidized to of phenol cause yield to improve.Liquid phase method is with liquid phase benzene and H
2O
2, O
2Deng reaction, under the condition of gentleness, generate phenol, have good prospects for commercial application.Many reports have been studied liquid phase benzene direct hydroxylation catalyst system, comprise the catalyzer such as heteropolyacid, HTS, loaded Cu, V, and are the most outstanding with vanadium series catalyst.
The vanadium sub-group compound catalyzer is the effective catalyst of unsaturated hydrocarbons hydroxylation reaction, (contains V such as famous Milas reagent
2O
5And H
2O
2) effectively catalysis carbon-carbon double bond hydroxylation change glycol (N.A.Milas, J.Am.Chem.Soc.59,2342,1937) into, it is high that vanadium replaces the heteropolyacid thermostability, has preferably catalytic activity, the invigorating grade of the Dalian Chemistry and Physics Institute is with solid [(CH
3)
4N]
4PMo
11VO
40For catalyzer carries out the reaction of heterogeneous benzene hydroxylation, the productive rate of phenol reaches 12.4% (invigorating etc., Catal.Commun.2008,9,728).The title complex of vanadium also has good catalytic activity and phenol selectivity, and in the product composition, phenol accounts for more than 97%, and does not generate benzoquinones, but the thermostability of catalyzer is not high, easily inactivation.Supported catalyst is owing to can reuse, and more with practical value, the molecular sieve that thermostability is high is a kind of suitable carrier, no matter loads on the vanadium species on molecular sieve surface or the skeleton, all to H
2O
2The Oxybenzene hydroxylation has good effect, such as V-MCM-41 (Y.W.Chen etc., Ind.Eng.Chem.Res, 1999,38 (5), 1983), VOx-MCM-41 (K.Lemke etc., Appl.Catal.A:Gen, 2003,243 (1), 41), but the selectivity of phenol is not high, and loss of active component is serious.
Catalyzer take transition metal complex as the direct hydroxylating of benzene also has partial monopoly and research paper report, and the research Fe (II) such as the yamashita of Japan (bipy)
3 2+The direct hydroxylating of benzene on the/Y zeolite heterogeneous catalyst, although selectivity can reach more than 99%, turn over number (every mol catalyzer generates phenol mol number) very low (H.Yamashita etc., J.Phys.Chem.C:112,2593).Bianchi etc. are studied the ligand effect of iron catalysis benzene hydroxylation reaction, and when adding without part, the phenol selectivity produces the carbonizing matter of about 10% biphenyl by product and 34% about 62%.After adding organic ligand, the selectivity of phenol is increased to 97～99%, in selected bitooth ligand, and the facilitation effect of N-O bitooth ligand best (2-methylpyrazine-5-carboxylic acid), calculating transformation frequency (TOF, mol product/mol iron * hour) with iron is 37h-1.And find, the N-N bitooth ligand is to H
2O
2Decomposing has restraining effect, and active minimum, the O-O bitooth ligand promotes H
2O
2Accelerate decomposition is unfavorable for the phenol selectivity.(the ./J.Mol.Catal A:Chem such as D.Bianchi, 204-205,2003,419).
Can find out from domestic and international research, vanadium replacement heteropolyacid thermostability is high, and the higher phenol selectivity of benzene transformation efficiency is not high, although transition metal complex Pyrogentisinic Acid's selectivity is very high, but active bad.
Summary of the invention
The object of the invention is to not high for the existing catalyzer synthetic yield that is applied to synthesizing phenol or selectivity is not high, the easy inactivation of heterogeneous catalyst, stability is not high, and the defective that work-ing life is long provides the heterogeneous catalyst for the synthesis of phenol of a kind of high reactivity and highly selective.
Heterogeneous catalyst for the synthesis of phenol of the present invention is a kind of schiff bases copper that is carried on silica-based molecular sieve/heteropolyacid super molecular compound, and its structural formula is:
Wherein, X
3Be one of following element or group: S, CONH-, OCO-, O;
X
1, X
2Be one of following element or group: F, Cl, Br, I, NO
2, R, C (CH
3)
3, COOR, OR, H;
Y is NHR or NR
2
Z is one of following radicals :-CH
2-(CH
2)
n-CH
2-C
6H
10Or C
6H
4, wherein, n=0 or 1;
POM is H
3+nPW
12-nV
nO
40Or H
3+nPMo
12-nV
nO
40, wherein, n=1～3;
Described R is CH
3Or C
2H
5Or C
3H
7
The present invention also aims to provide a kind of preparation method of above-mentioned heterogeneous catalyst for the synthesis of phenol, it comprises the step of following order:
(1) modified with functional group of carrier:
By 1 gram MCM-41/0.016～0.03mol silane coupling agent X
3-CH
2CH
2CH
2Si (OMe)
3The ratio of the dried toluene of/5～10mL makes the three be mixed into suspension, at N
2The lower backflow 48h of protection, solid filtering also carries out Soxhlet with methylene dichloride and extracts 24h, gets X
3-MCM-41;
The preparation of (2) load schiff bases copper complex:
Substituted salicylic aldehydes by behind the prior art chlorine formylation, is got substituted salicylic aldehydes allyl alcohol ether with vinyl carbinol by 1: 1 mol ratio backflow 24h in dimethylbenzene again; Again by 1 gram X
3The ratio of the quadrol of-MCM-41/0.016～0.03mol substituted salicylic aldehydes allyl alcohol ether/0.016～0.03mol or propylene diamine or cyclohexanediamine or O-Phenylene Diamine/another substituted salicylic aldehydes of 0.016～0.03mol is mixed into suspension take dimethylbenzene as solvent with four, and reaction 24h gets the load part; Load part and cupric nitrate react 20h, CH by 1: 1 mol ratio in anhydrous methanol
2Cl
2The Soxhlet extracting, the dry load schiff bases copper complex that gets;
(3) be carried on the supramolecule combination of copper complex and the heteropolyacid of silica-based molecular sieve:
With prepared supported copper presence of Schiff-base complex of (2) step and H
3+nPMo
12-nV
nO
40(n=1～3) or H
3+nPW
12-nV
nO
40(n=1～3) heteropolyacid stirred 24 hours by 1: 1 mixed in molar ratio in anhydrous methanol, filters, and washing, vacuum-drying obtains heterogeneous catalyst.
The present invention also aims to provide the above-mentioned application of heterogeneous catalyst in the reaction of benzene direct oxidation synthesizing phenol for the synthesis of phenol.This catalyzer is applied to benzene and molecular oxygen or 30%H
2O
2Direct oxidation reaction, reaction formula is as follows:
Described application is: with above-mentioned heterogeneous catalyst and benzene, 30% H
2O
2, anhydrous acetonitrile mixes in three-necked bottle by 1～4%, 5～8%, 12～18%, 70～82% mass percent respectively, and prolong and thermometer are installed, and adopts magnetic agitation; After temperature rises to 60～75 ℃, reacted 6 hours; Cooling, filtering catalyst is collected filtrate, and filtrate is used gas chromatographic analysis, is calculated phenol yield; Filtrate is removed acetonitrile and remaining benzene by distillation method, thereby obtains purified petroleum benzin phenol.
Described application can also be: with above-mentioned heterogeneous catalyst and benzene, xitix, Glacial acetic acid, H
2O joins in the autoclave by 1～4%, 5～8%, 7～10%, 60～72%, 15～20% mass percent respectively, oxygen and nitrogen to the 2～6MPa of logical 3: 1～5: 1 volume ratios, and temperature of reaction is 60～90 ℃, reaction 2～6h; Autoclave is cooled to room temperature, emits residual gas, filtering catalyst is collected filtrate, and filtrate is used gas chromatographic analysis, calculated phenol yield; Obtain purified petroleum benzin phenol after the filtrate distillation.
The supported catalyst that contains four tooth N-O schiff bases copper complexes and heteropolyacid of the present invention is applicable to liquid phase benzene and molecular oxygen or H
2O
2The direct oxidation synthesizing phenol.This catalyzer and reported in literature result compare, and benzene transformation efficiency and phenol selectivity have had large increase, easy and product separation after the reaction, and catalyst life is long, has reactive behavior high, and the phenol selectivity is good, and catalyzer is without characteristics such as losses.
Embodiment
The present invention is described in further detail below in conjunction with concrete experiment embodiment.
Example 1:Cu
II(salen)-PMo
11The preparation of V/MCM-41 (salen=double salicylaldehyde contracting quadrol).
(1) adopt literature method to prepare the 5-chloromethyl salicylaldehyde, yield is 40～60%.(Sun Zhenhua etc., Liaoning chemical industry, 2010,39 (5) 461)
(2) 5-chloromethyl salicylaldehyde and vinyl carbinol get salicylic aldehyde-5-methoxy allyl alcohol ether by 1: 1 mol ratio backflow 24h in dimethylbenzene.
(3) 1 gram MCM-41,0.016mol 3-mercaptopropyl trimethoxysilane are mixed in dried toluene, the concentration of 3-mercaptopropyl trimethoxysilane in dried toluene is 1.6mol/L.Mixed solution is at N
2The lower backflow 48h of protection, solid filtering also carries out Soxhlet with methylene dichloride and extracts 24h, gets SH-MCM-41.With 1gSH-MCM-41,5mmol salicylic aldehyde-5-methoxy allyl alcohol ether, 5mmol 5-dimethylamino salicylic aldehyde, 5mmol quadrol in CH
2Cl
2Middle mixing, reaction 24h gets load salen part.With load salen part and Cu (NO
3)
2By 1: 1 mol ratio 30 ℃ of lower reaction 20h in anhydrous methanol, get supported copper salen title complex.According to the thermogravimetric detected result, 1g load salen part approximately contains salen part 2.85mmol.
(4) supported copper salen title complex and H
4PMo
11VO
40In the anhydrous methanol with the HCl acidifying, react 24h by 1: 1 mol ratio, filter CH
2Cl
2Washing, vacuum-drying gets heterogeneous catalyst.
Net reaction is as follows:
(5) with the Cu for preparing
II(salen)-PMo
11V/MCM-4, benzene, 30%H
2O
2, anhydrous acetonitrile is by 2: 6: 14: 78 mass ratio is added in the three-necked bottle, and prolong and thermometer are installed, and adopts magnetic agitation.After temperature rises to 65 ℃, react cooling after 6 hours, filtering catalyst is collected filtrate, uses gas chromatographic analysis filtrate, and the productive rate that obtains phenol is 16.4%, and selectivity is 91.2%.
(6) get the Cu of preparation
II(salen)-PMo
11V/MCM-41, benzene, xitix, Glacial acetic acid, H
2O was by 2: 6: 8: 65: 19 mass ratio joins in the autoclave, the oxygen of logical 3: 1 volume ratios and nitrogen are to 3.5MPa, 60 ℃ of temperature of reaction, reaction 3h is cooled to room temperature with autoclave, emits residual gas, filtering catalyst, filtrate is used gas chromatographic analysis, and the productive rate that obtains phenol is 13.7%, and selectivity is 94.6%.
Example 2:Cu
II(salen)-PMo
10V
2The preparation of/MCM-41 (salen=double salicylaldehyde contracting quadrol).
The step of this example (1)-(3) are identical with step (1)-(3) of example 1.
(4) step was: supported copper salen title complex and H
5PMo
10V
2O
40In the anhydrous methanol with the HCl acidifying, react 24h by 1: 1 mol ratio, filter CH
2Cl
2Washing, vacuum-drying gets heterogeneous catalyst.
(5) get the Cu of preparation
II(salen)-PMo
10V
2/ MCM-41, benzene, 30%H
2O
2, anhydrous acetonitrile is by 2: 6: 14: 78 mass ratio is added in the three-necked bottle, and prolong and thermometer are installed, and adopts magnetic agitation.After temperature rises to 65 ℃, reacted 6 hours, filtering catalyst is collected filtrate, uses gas chromatographic analysis, and the productive rate that obtains phenol is 14.8%, and selectivity is 90.5%.
(6) get the Cu of preparation
II(salen)-PMo
10V
2/ MCM-41 benzene, xitix, Glacial acetic acid, H
2O was by 2: 6: 8: 65: 19 mass ratio joins in the autoclave, the oxygen of logical 3: 1 volume ratios and nitrogen are to 3.5MPa, 60 ℃ of temperature of reaction, reaction 3h is cooled to room temperature with autoclave, emits residual gas, filtering catalyst, filtrate is used gas chromatographic analysis, and the productive rate that obtains phenol is 12.2%, and selectivity is 94.7%.
Example 3:Cu
II(saloph)-PMo
11The preparation of V/MCM-41 (saloph=double salicylaldehyde contracting O-Phenylene Diamine).
The step of this example (1)-(2) are identical with step (1)-(2) of example 1.
(3) step was: 1 gram MCM-41,0.016mol 3-mercaptopropyl trimethoxysilane are mixed in dried toluene, and the concentration of 3-mercaptopropyl trimethoxysilane in dried toluene is 1.6mol/L.Mixed solution is at N
2The lower backflow 48h of protection, solid filtering also carries out Soxhlet with methylene dichloride and extracts 24h, gets SH-MCM-41.1 gram SH-MCM-41 and 5mmol salicylic aldehyde-5-methoxy allyl alcohol ether are mixed in dimethylbenzene, approximately contain salicylic aldehyde 3mmol in the dried solid of 1 gram.Add again and the CH of the contained salicylic aldehyde of drying solid equimolar 5-dimethylamino salicylic aldehyde and O-Phenylene Diamine
2Cl
2Solution, at room temperature stirring reaction 24h obtains load saloph part, and thermogravimetric result shows in every gram load saloph part and contains saloph part 2.6mmol.Load saloph part and Cu (NO
3)
2By 1: 1 mol ratio 30 ℃ of lower reaction 20h in anhydrous methanol, get supported copper saloph title complex.
(4) supported copper saloph title complex again and H
4PMo
11VO
40In HCl acidifying anhydrous methanol, react 24h by 1: 1 mol ratio, filter CH
2Cl
2Washing, vacuum-drying gets Cu
II(saloph)-PMo
11The V/MCM-41 heterogeneous catalyst.
(5) get the Cu of preparation
II(saloph)-PMo
11V/MCM-41, benzene, 30%H
2O
2, anhydrous acetonitrile is by 2: 6: 14: 78 mass ratio is added in the three-necked bottle, and prolong and thermometer are installed, and adopts magnetic agitation.After temperature rises to 65 ℃,, react after 6 hours, filtering catalyst is collected filtrate, uses gas chromatographic analysis filtrate, and the productive rate that obtains phenol is 17.8%, and selectivity is 90.2%.
(6) get the Cu of preparation
II(saloph)-PMo
11V/MCM-41, benzene, xitix, Glacial acetic acid, H
2O was by 2: 6: 8: 65: 19 mass ratio joins in the autoclave, the oxygen of logical 3: 1 volume ratios and nitrogen are to 3.5MPa, 60 ℃ of temperature of reaction, behind the reaction 3h, autoclave is cooled to room temperature, emits residual gas, filtering catalyst, filtrate is used gas chromatographic analysis, and the productive rate that obtains phenol is 11.4%, and selectivity is 92.8%.
Example 4:Cu
II(saloph)-PMo
10V
2The preparation of/MCM-41 (saloph=double salicylaldehyde contracting O-Phenylene Diamine).
This example prepares loaded Cu
II(saloph) step of title complex (1)-(3) are identical with step (1)-(3) of example 3.
Step (4) is: supported copper saloph title complex again and H
5PMo
10V
2O
40In HCl acidifying anhydrous methanol, react 24h by 1: 1 mol ratio, filter CH
2Cl
2Washing, vacuum-drying gets Cu
II(saloph)-PMo
10V
2/ MCM-41 heterogeneous catalyst.
(5) get the Cu of preparation
II(saloph)-PMo
10V
2/ MCM-41, benzene, 30%H
2O
2, anhydrous acetonitrile is by 2: 6: 14: 78 mass ratio is added in the three-necked bottle, and prolong and thermometer are installed, and adopts magnetic agitation.After temperature rises to 65 ℃, react after 6 hours, filtering catalyst is collected filtrate, uses gas chromatographic analysis filtrate, and the productive rate that obtains phenol is 17.7%, and selectivity is 91.3%.
(6) get the Cu of preparation
II(saloph)-PMo
10V
2/ MCM-41, benzene, xitix, Glacial acetic acid, H
2O was by 2: 6: 8: 65: 19 mass ratio adds in the autoclave, the oxygen of logical 3: 1 volume ratios and nitrogen are to 3.5MPa, 60 ℃ of temperature of reaction, behind the reaction 3h, autoclave is cooled to room temperature, emits residual gas, filtering catalyst, filtrate is used gas chromatographic analysis, and the productive rate that obtains phenol is 15.4%, and selectivity is 92.8%.
Example 5: contrast experiment.
(1) Cu
IIThe preparation of salen title complex.
Salicylic aldehyde and quadrol react at anhydrous methanol by 2: 1 mol ratios, are heated to 60 ℃, and the triethylamine of adding and quadrol equimolar amount is catalyzer, reacted 2 hours, to producing yellow or orange-yellow precipitation, suction filtration, use ethyl alcohol recrystallization, get needle-like Schiff base ligand crystal.Part uses anhydrous alcohol solution and cupric nitrate ethanolic soln with 1: 1 mixed in molar ratio, and 70 ℃ of lower reactions 4 hours produce brown precipitate, obtain Cu
IISalen title complex, productive rate are 45%.
(2) get the Cu of preparation
IISalen title complex, benzene, 30%H
2O
2, anhydrous acetonitrile is by 0.5: 6: 14: 79.5 mass ratioes are installed prolong and thermometer in three-necked bottle, adopt magnetic agitation.After temperature rises to 65 ℃, react after 6 hours, cooling, filtering catalyst is collected filtrate, uses gas chromatographic analysis, and the productive rate that obtains phenol is 3.5%, and selectivity is 88.3%.
(3) get the Cu of preparation
IISalen title complex, benzene, xitix, Glacial acetic acid, H
2O was by 0.4: 5: 8: mass ratio joined in the autoclave in 66: 20.6, the oxygen of logical 3: 1 volume ratios and nitrogen are to 3.5MPa, 60 ℃ of temperature of reaction, behind the reaction 3h, autoclave is cooled to room temperature, emits residual gas, filtering catalyst, filtrate is used gas chromatographic analysis, and the productive rate that obtains phenol is 3.2%, and selectivity is 82.8%.
Example 6: contrast experiment.
(1) Cu
IIThe preparation of saloph title complex.
Salicylic aldehyde and quadrol react at anhydrous methanol by 2: 1 mol ratios, are heated to 60 ℃, and adding the 1mmol triethylamine is catalyzer, react 2 hours, and to producing yellow or orange-yellow precipitation, suction filtration is used ethyl alcohol recrystallization, gets needle-like Schiff base ligand crystal.Part uses anhydrous alcohol solution and cupric nitrate ethanolic soln with 1: 1 mixed in molar ratio, and 70 ℃ of lower reactions 4 hours produce brown precipitate, obtain Cu
IISalen title complex, productive rate are 45%.
(2) get the Cu of preparation
IISaloph title complex, benzene, 30%H
2O
2, anhydrous acetonitrile is by 0.5: 6: 14: 79.5 mass ratioes are installed prolong and thermometer in three-necked bottle, adopt magnetic agitation.After temperature rises to 70 ℃, react after 6 hours, cooling, filtering catalyst is collected filtrate, gas chromatographic analysis, the productive rate that obtains phenol is 5.8%, selectivity is 88.6%.
(3) get the Cu of preparation
IISalen title complex benzene, xitix, Glacial acetic acid, H
2O was by 0.4: 5: 8: mass ratio joined in the autoclave in 66: 20.6, the oxygen of logical 3: 1 volume ratios and nitrogen are to 3.5MPa, 60 ℃ of temperature of reaction, behind the reaction 3h, autoclave is cooled to room temperature, emits residual gas, filtering catalyst, filtrate is used gas chromatographic analysis, and the productive rate that obtains phenol is 4.6%, and selectivity is 82.3%.
Example 7: contrast experiment.
(1) load P Mo
11The preparation of V/MCM-41.
In the ratio of 1g MCM-41/0.9mmol coupling agent/0.9mmol heteropolyacid, make MCM-41, γ-aminopropyl triethoxysilane (AMPTS), heteropolyacid (H
4PMo
11VO
40) at ethanol/H of 1: 1 of volume ratio
2Mix among the O, stirring and refluxing 24h filters, and the washing final vacuum is dry.
(2) get the PMo of preparation
11V/MCM-41, benzene, 30%H
2O
2, anhydrous acetonitrile is by 2: 6: 14: 78 mass ratio is added in the three-necked bottle, and prolong and thermometer are installed, and adopts magnetic agitation.After temperature rises to 65 ℃, drip H
2O
2Acetonitrile solution reacted after 6 hours, and filtering catalyst is collected filtrate, gas chromatographic analysis, and the productive rate that obtains phenol is 9.8%, selectivity is 84.2%.
(3) get the PMo of preparation
11V/MCM-41, benzene, xitix, Glacial acetic acid, H
2O was by 2: 6: 8: 65: 19 mass ratio joins in the autoclave, the oxygen of logical 3: 1 volume ratios and nitrogen are to 3.5MPa, 60 ℃ of temperature of reaction, behind the reaction 3h, autoclave is cooled to room temperature, emits residual gas, filtering catalyst, filtrate is used gas chromatographic analysis, and the productive rate that obtains phenol is 7.6%, and selectivity is 81.6%.
Can find out from above contrast experiment, the prepared supported copper composition catalyst of the present invention is with respect to the loaded by heteropoly acid catalyzer, and activity significantly improves, and productive rate and the selectivity of phenol also are greatly improved.In addition, the result of embodiment is as shown in the table under other conditions of the present invention.
Subordinate list 1: with 30%H
2O
2During for oxygenant, catalytic result under the differential responses condition
Subordinate list 2: with O
2Be oxygenant, logical 4: 1 O
2/ N
2During to 3.5MPa, different proportioning catalytic results
Claims (5)
1. heterogeneous catalyst for the synthesis of phenol is a kind of schiff bases copper that is carried on silica-based molecular sieve/heteropolyacid super molecular compound, and its structural formula is:
Wherein, X
3Be one of following element or group: S, CONH-, OCO-, O;
X
1, X
2Be one of following element or group: F, Cl, Br, I, NO
2, R, C (CH
3)
3, COOR, OR, H; Described R is a kind of of alkyl, is specially CH
3Or C
2H
5Or C
3H
7
Y is NHR or NR
2
Z is one of following radicals :-CH
2-(CH
2)
n-CH
2-, C
6H
10Or C
6H
4, wherein, n=0 or 1;
POM is H
3+nPW
12-nV
nO
40Or H
3+nPMo
12-nV
nO
40, wherein, n=1～3;
Described R is CH
3Or C
2H
5Or C
3H
7
2. one kind as claimed in claim 1 for the synthesis of the preparation method of the heterogeneous catalyst of phenol, it is characterized in that comprising the step of following order:
(1) modified with functional group of carrier:
By 1 gram MCM-41/0.016～0.03mol silane coupling agent X
3-CH
2CH
2CH
2Si (OMe)
3The ratio of the dried toluene of/5～10mL makes the three be mixed into suspension, at N
2The lower backflow 48h of protection, solid filtering also carries out Soxhlet with methylene dichloride and extracts 24h, gets X
3-MCM-41;
The preparation of (2) load schiff bases copper complex:
Substituted salicylic aldehydes by behind the prior art chlorine formylation, is got substituted salicylic aldehydes allyl alcohol ether with vinyl carbinol by 1:1 mol ratio backflow 24h in dimethylbenzene again; Again by 1 gram X
3The ratio of the quadrol of-MCM-41/0.016～0.03mol substituted salicylic aldehydes allyl alcohol ether/0.016～0.03mol or propylene diamine or cyclohexanediamine or O-Phenylene Diamine/another substituted salicylic aldehydes of 0.016～0.03mol is mixed into suspension take dimethylbenzene as solvent with four, and reaction 24h gets the load part; Load part and cupric nitrate react 20h, CH by the 1:1 mol ratio in anhydrous methanol
2Cl
2The Soxhlet extracting, the dry load schiff bases copper complex that gets;
Wherein, the substituted salicylic aldehydes structural formula is:
X
1, X
2Be one of following element or group: F, Cl, Br, I, NO
2, R, C (CH
3)
3, COOR, OR, H; Described R is a kind of of alkyl, is specially CH
3Or C
2H
5Or C
3H
7
(3) be carried on the supramolecule combination of copper complex and the heteropolyacid of silica-based molecular sieve:
With prepared load schiff bases copper complex of (2) step and H
3+nPMo
12-nV
nO
40(n=1～3) or H
3+nPW
12-nV
nO
40(n=1～3) heteropolyacid is pressed the 1:1 mixed in molar ratio and was stirred 24 hours in anhydrous methanol, filters, and washing, vacuum-drying obtains heterogeneous catalyst.
3. one kind as claimed in claim 1 for the synthesis of the application in the reaction of benzene direct oxidation synthesizing phenol of the heterogeneous catalyst of phenol.
4. the according to claim 3 described application of heterogeneous catalyst in the reaction of benzene direct oxidation synthesizing phenol for the synthesis of phenol is characterized in that comprising following process:
With heterogeneous catalyst claimed in claim 1 and benzene, 30% H
2O
2, anhydrous acetonitrile mixes in three-necked bottle by 1～4%, 5～8%, 12～18%, 70～82% mass percent respectively, and prolong and thermometer are installed, and adopts magnetic agitation; After temperature rises to 60～75 ℃, reacted 6 hours; Cooling, filtering catalyst is collected filtrate, and filtrate is used gas chromatographic analysis, is calculated phenol yield; Filtrate is removed acetonitrile and remaining benzene by distillation method, thereby obtains purified petroleum benzin phenol.
5. the according to claim 3 described application of heterogeneous catalyst in the reaction of benzene direct oxidation synthesizing phenol for the synthesis of phenol is characterized in that comprising following process:
With heterogeneous catalyst claimed in claim 1 and benzene, xitix, Glacial acetic acid, H
2O joins in the autoclave by 1～4%, 5～8%, 7～10%, 60～72%, 15～20% mass percent respectively, oxygen and nitrogen to the 2～6MPa of logical 3:1～5:1 volume ratio, and temperature of reaction is 60～90 ℃, reaction 2～6h; Autoclave is cooled to room temperature, emits residual gas, filtering catalyst is collected filtrate, and filtrate is used gas chromatographic analysis, calculated phenol yield; Obtain purified petroleum benzin phenol after the filtrate distillation.
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| US4215226A (en) * | 1978-11-06 | 1980-07-29 | Gulf Research & Development Company | Selective hydrogenation of nitroaromatic acetylenes over an unsupported RuS2 catalyst |
| EP1325901A1 (en) * | 2002-01-04 | 2003-07-09 | Council of Scientific and Industrial Research | An improved process for the preparation of adipic acid |
| CN101306386A (en) * | 2008-07-04 | 2008-11-19 | 华中科技大学 | Palladium catalyst for synthesizing oxalate using liquid phase coupling method and use thereof |
| CN101912788A (en) * | 2010-07-31 | 2010-12-15 | 太原理工大学 | Amino-containing resorcin aluminum bifunctional catalyst as well as synthetic method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4215226A (en) * | 1978-11-06 | 1980-07-29 | Gulf Research & Development Company | Selective hydrogenation of nitroaromatic acetylenes over an unsupported RuS2 catalyst |
| EP1325901A1 (en) * | 2002-01-04 | 2003-07-09 | Council of Scientific and Industrial Research | An improved process for the preparation of adipic acid |
| CN101306386A (en) * | 2008-07-04 | 2008-11-19 | 华中科技大学 | Palladium catalyst for synthesizing oxalate using liquid phase coupling method and use thereof |
| CN101912788A (en) * | 2010-07-31 | 2010-12-15 | 太原理工大学 | Amino-containing resorcin aluminum bifunctional catalyst as well as synthetic method and application thereof |
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