CN102731234A - CO (carbon monoxide)-promoted method for directly oxygenizing hydroxylated aromatic compound by molecular oxygen - Google Patents

CO (carbon monoxide)-promoted method for directly oxygenizing hydroxylated aromatic compound by molecular oxygen Download PDF

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CN102731234A
CN102731234A CN2012102302469A CN201210230246A CN102731234A CN 102731234 A CN102731234 A CN 102731234A CN 2012102302469 A CN2012102302469 A CN 2012102302469A CN 201210230246 A CN201210230246 A CN 201210230246A CN 102731234 A CN102731234 A CN 102731234A
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carbon monoxide
noble metal
metal catalyst
benzene
selectivity
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曹勇
倪吉
于磊
刘永梅
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Fudan University
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Fudan University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention belongs to the technical field of the catalytic synthesis, and particularly discloses a CO (carbon monoxide)-promoted method for directly oxygenizing a hydroxylated aromatic compound by molecular oxygen. The method provided by the invention uses an aromatic compound as a substrate, uses a combined catalyst consisting of a supported precious metal catalyst and a heteroatom zeolite containing Ti, V, Cu or Fe or a polyoxometalate, and uses the mixed liquid of water and an organic solvent as a solvent; the CO (carbon monoxide) and O2 (oxygen) are put into the reaction system; and, under the promotion of the CO (carbon monoxide), the molecular oxygen directly oxygenizes the hydroxylated aromatic compound to prepare a corresponding phenol compound. The equipment and the process used by the method provided by the invention are simple; the separation of the target product is relatively easy; the reaction conditions are moderate; the system is environment-friendly; and thus the method is a green process route.

Description

The method of the promoted molecular oxygen direct oxidation of a kind of CO hydroxylation aromatic hydroxy compound
Technical field
The invention belongs to the catalytic synthetic techniques field, be specifically related to the method for the direct hydroxylation of a kind of aromatic hydroxy compound.
Background technology
The hydroxylation product of aromatic hydroxy compound is a compound important in chemical industry and the pharmacy field.For example: methyl paraben is a medicine, food, and spices, the anticorrosive additive in the film also is a strong fungicide.Yet at present the hydroxylation product overwhelming majority of aromatic compound is via polystep reaction method system, and its process is complicated, and is high to equipment requirements, unfavorable to producing.The phenol of one of aromatic hydrocarbons hydroxylation product is a kind of crucial large Organic Chemicals, in medicine intermediate, agricultural chemicals, spices, dyestuff, auxiliary agent, resin field wide application is arranged.The main working method of phenol is the cumene oxidation method at present, this method experience three-step reaction, and major defect is complicated with technology, and energy consumption is high, and serious to equipment corrosion, particularly its by product acetone demand is far below phenol.Therefore, research receives extensive concern by the novel process of the direct hydroxylation system phenolic cpd of aromatic compound.
The novel process of existing one step of benzene hydroxylation system phenol if divide by employed oxygenant, then is that the correlative study of oxygenant is maximum with the hydrogen peroxide.Document (K.M. Parida, D. Rath, Appl. Catal. A:Gen., 321 (2007): be catalyzer 101-108) with Cu/MCM-41, liquid phase synthesizing phenol in acetic acid, the transformation efficiency of benzene and phenol selectivity are respectively 21% and 94%.In addition, Chinese patent CN129961C discloses with acid-treated activated carbon catalyst, and under liquid-phase reaction condition, the benzene transformation efficiency is 11-13%.In addition with N 2O is that oxygenant also has some reports.Document (D. Meloni, R. Monaci, V. Solinas, et al, J. Catal., 314 (2003): be catalyzer 169-178) with the Fe-MFI molecular sieve, the gas-phase reaction synthesizing phenol, temperature of reaction is 400 oUnder the C, the transformation efficiency of benzene and phenol selectivity are respectively 20% and 90%.Aforesaid method is compared with traditional method, though simplified technology, has improved atom utilization, and main deficiency is N 2O and hydrogen peroxide price are expensive, and not high based on the phenol selectivity of oxygenant.
Is that oxygenant realizes that the direct hydroxylation of phenyl ring is the target in industry member and the academic research with the molecular oxygen all the time, is considered to the greatly challenging problem of tool of catalytic field ten.As far back as 1888, it was oxygenant that Friedel and Crafts have just attempted with oxygen, and aluminum chloride is a catalyzer, the direct hydroxylation research of the benzene under the gas-phase reaction condition.Hereafter; With molybdenum, tungsten, copper or vanadium sill is that the research of catalyzer emerges in an endless stream document (H. Yamanaka, R. Hamada; H. Nibuta; Et al, J. Mol. Catal. A:Chemical, 178 (2002): be that the phenol yield of catalyzer gained is 1.5% with Cu/ZSM-5 89-95); Document (Y. Liu, K. Murata, M. Inaba, Catal. Commun., 6 (2005): 679-683) with [(C 4H 9) 4N] 5[PW 11CuO 39(H 2O)] be catalyzer, the liquid-phase oxidation benzene synthesizing phenol, the transformation efficiency of benzene and the selectivity of phenol are respectively 9.2% and 91.8%.When being oxygenant with the molecular oxygen, though it is cheap, the transformation efficiency of benzene is lower, is no more than 20 % usually.To being oxygenant with the molecular oxygen, the problem low, document (S. Niwa, M. Eswaramoorthy to the benzene oxidation capacity; J. Nair, et al, Science; 295 (2002): be catalyzer with the palladium film 105-107), oxygen is oxygen source, and hydrogen is auxiliary agent; Benzene feedstock can be converted into phenol in fixed-bed reactor, but the transformation efficiency of benzene is not high, and hydrogen Pyrogentisinic Acid's selectivity is lower.In addition, document (S.L. Shu, Y. Huang; X.J. Hu; J. Phys. Chem. C, 113 (2009): 19618-19622) think that through experiment repeatedly above-mentioned palladium film catalyst does not have the performance of the direct hydroxylation of catalysis benzene under this reaction conditions; And the hydrogen that takes place at catalyst surface and the combustion reactions of oxygen very easily cause the damage of film catalyst structure, and be unfavorable to the catalyst stability ten minutes.Therefore the application prospect that with hydrogen is the direct dihydroxylation process of molecular oxygen oxidation benzene of auxiliary agent remains to be discussed.
Summary of the invention
The object of the present invention is to provide the novel method of the direct hydroxylation system phenolic compound of a kind of aromatic hydrocarbons, to overcome existing problem in the existing aromatic hydrocarbons hydroxylation technology.
Solution provided by the invention is: be substrate with the aromatic hydroxy compound, use by loaded noble metal catalyst with contain the hetero-atom molecular-sieve of Ti, V, Cu or Fe or the combination catalyst that heteropolyacid salt is formed, be solvent with the mixed solution of water and organic solvent; Feed CO and O 2, CO and O 2Pressing force is than being 0.1:1～9:1, and total pressure is 0.5～3 MPa; Under CO promoted, by molecular oxygen direct oxidation hydroxylation aromatic hydroxy compound, temperature of reaction was 20-150 OC, make the corresponding phenolic compound; Wherein, said substrate and solvent are 0.01:1～0.2:1 by mass ratio.
Among the present invention, the metal in the said loaded noble metal catalyst is selected from one or more among Pt, Pd, Rh, Ru, Ir, Au or the Ag, and carrier is selected from TiO 2, CeO 2, Fe 2O 3, Al 2O 3And ZrO 2In one or more.Described loaded noble metal catalyst can prepare through following method: coprecipitation method, deposition-precipitation method, colloid method or pickling process.
Among the present invention; Contain the hetero-atom molecular-sieve of Ti, V, Cu or Fe or the silicon oxide molecular sieve that heteropolyacid salt is selected from the MFI, MWW, MCM, HMS, Beta or the SBA configuration that contain Ti, V, Cu or Fe, contain the aluminium phosphate molecular sieve of Cu and contain the tungstate of V or in the molybdate one or more.
The mol ratio of noble metal catalyst is 50:1～1000:1 in said substrate and the combination catalyst; In the combination catalyst, the mass ratio of said loaded noble metal catalyst and said hetero-atom molecular-sieve or heteropolyacid salt is 0.5:1～2:1.
Among the present invention, reaction solvent is the mixed solvent of organic solvent and water, and described organic solvent is selected from methyl alcohol, acetone, acetonitrile or acetate; Organic solvent and water are 1:9～9:1 by volume in the said mixed solvent.
Among the present invention, said aromatic hydroxy compound is replacement/unsubstituted benzene and replacement/unsubstituted condensed-nuclei aromatics.Described substituting group is one or more in alkyl, alkoxyl group, hydroxyl, fluorine, chlorine, bromine, iodine, cyanic acid, acyl group, trifluoromethyl, nitro or the carboxyl.
Than existing method, the present invention has following advantage: environmental friendliness, and the reaction corrosion is little, and it is light that the three wastes are handled burden, can satisfy the requirement of cleaner production, helps scale operation; Reaction conditions is gentle, is a friendly process route.Employed catalyzer is heterogeneous catalyst, and is simple to operate, and product and catalyst separating are easy.
Embodiment
Through embodiment the present invention is detailed further below, but content of the present invention is not limited thereto.
Embodiment 1:Take by weighing 0.664 g H 2PtCl 69H 2O, 0.420 g PdCl 2, 0.508 g RhCl 3, 0.646 g RuCl 33H 2O, 0.670 g H 2IrCl 66H 2O or 0.390 g AgNO 3Drop into respectively in 6 100 mL beakers, add 5 g ZrO more respectively 2With 20 mL water, stir following 80 oCareful evaporate to dryness water in the C water-bath, the sample of gained is 100 oBaking is 12 hours in the C baking oven, and solid is changed in the crucible 350 oGet down from horse not kiln roasting 2 hours of C is again at 5% H 2In/Ar the air-flow 300 oRoasting is after 2 hours under the C.Make catalyzer after the cooling, be expressed as Pt/ZrO 2-Im, Pd/ZrO 2-Im, Rh/ZrO 2-Im, Ru/ZrO 2-Im, Ir/ZrO 2-Im or Ag/ZrO 2-Im.
Embodiment 2:Take by weighing 0.664 g H 2PtCl 69H 2O or 0.420 g PdCl 2Drop into 2 respectively and fill in the 100 mL beakers, add 5 g TiO again 2With the ethylene glycol solution of 40 mL 0.25M NaOH, stir after 1 hour under the room temperature, temperature is risen to 140 oC continue to stir 3 hours, with sedimentation and filtration, with distilled water wash 3 times, 100 oC dry 12 hours down makes catalyzer after the cooling, be expressed as Pt/TiO 2-CD or Pd/TiO 2-CD.
Embodiment 3:With 0.104 g HAuCl 44H 2O, 0.5 L water drop in the 1 L beaker, and 80 oThe sodium hydroxide solution that splashes into concentration under the C agitation condition and be 0.2 M to pH be about 7, drop into 5 g CeO again 2, 80 oC continues down to stir 2 hours, with sedimentation and filtration, is washed with distilled water to no Cl -, 100 oC dry 12 hours down is at last 300 oThe retort furnace roasting is 4 hours under the C.Make catalyzer after the cooling, be expressed as Au/CeO 2-DP.
Embodiment 4:With 0.468 g HAuCl 44H 2O, 12.65 g Fe (NO 3) 39H 2O, 0.5 L water drop in the 1 L beaker, and 80 oThe sodium hydroxide solution that splashes into concentration under the C agitation condition and be 0.2 M to pH be about 8, continue to stir 30 minutes, with sedimentation and filtration, be washed with distilled water to no Cl -, 100 oC dry 12 hours down is at last 300 oThe retort furnace roasting is 4 hours under the C.Make catalyzer after the cooling, be expressed as Au/Fe 2O 3-CP.
Embodiment 5:Catalyzer 0.1 g, 0.1 g Ti-MWW molecular sieve and 2 mmol benzene inputs prepared among the weighing embodiment 1 to embodiment 4 fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetone; With after the carbon monoxide displacement autoclave air, the autoclave internal temperature is appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.Benzene transformation efficiency, phenol selectivity and Resorcinol selectivity are seen table 1.
 
Table 1 embodiment 5 results
Loaded noble metal catalyst Benzene transformation efficiency % Phenol selectivity % Resorcinol selectivity %
Pt/ZrO 2-Im 58 92 8
Pd/ZrO 2-Im 56 93 7
Rh/ZrO 2-Im 32 96 4
Ru/ZrO 2-Im 31 95 5
Ir/ZrO 2-Im 47 95 4
Ag/ZrO 2-Im 13 97 3
Pt/TiO 2-CD 42 94 6
Pd/TiO 2-CD 47 94 6
Au/CeO 2-DP 45 94 6
Au/Fe 2O 3-CP 36 95 5
Embodiment 6:Weighing 0.1 g Pt/ZrO 2-Im, 0.1 g Ti-MWW molecular sieve and 2 mmol benzene inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetone, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 40 respectively then oC, 50 oC, 60 oC, 70 OCOr 80 oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.Benzene transformation efficiency, phenol selectivity and Resorcinol selectivity are seen table 2.
Table 2 embodiment 6 results
Temperature of reaction oC Benzene transformation efficiency % Phenol selectivity % Resorcinol selectivity %
40 31 97 3
50 37 97 3
60 42 95 5
70 49 94 6
80 58 92 8
Embodiment 7:Weighing 0.1 g Pt/ZrO 2-Im, 0.1 g Ti-MWW molecular sieve and 2 mmol benzene inputs fill organic solvent (methyl alcohol, acetone or acetonitrile) and water in the 100 mL stainless steel autoclaves of totally 10 mL; The volume ratio of organic solvent and water is respectively 1:2,1:1 or 2:1; With after the carbon monoxide displacement autoclave air, the autoclave internal temperature is appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.Benzene transformation efficiency, phenol selectivity and Resorcinol selectivity are seen table 3.
Table 3 embodiment 8 results
Water mL Organic solvent/volume mL Benzene transformation efficiency % Phenol selectivity % Resorcinol selectivity %
3.3 Methyl alcohol/6.7 39 97 3
5 Methyl alcohol/5 53 93 7
6.7 Methyl alcohol/3.3 45 96 4
3.3 Acetone/6.7 55 94 6
5 Acetone/5 58 92 8
6.7 Acetone/3.3 45 96 4
3.3 Acetonitrile/6.7 32 95 5
5 Acetonitrile/5 44 95 5
6.7 Acetonitrile 3.3 48 94 6
Embodiment 9:Weighing 0.1 g Pt/ZrO 2-Im, 0.1 g Ti-MWW molecular sieve and 2 mmol benzene inputs fill respectively in the 100 mL stainless steel autoclaves of water that 5 mL, 8 mL, 10 mL, 15 mL or 20 mL volume ratios are 1:1 and acetone mixed solvent; With after the carbon monoxide displacement autoclave air, the autoclave internal temperature is appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.Benzene transformation efficiency, phenol selectivity and Resorcinol selectivity are seen table 4.
Table 4 embodiment 9 results
Solvent volume mL Benzene transformation efficiency % Phenol selectivity % Resorcinol selectivity %
5 56 91 9
8 57 92 8
10 58 92 8
15 51 94 6
20 46 94 6
Embodiment 10:Weighing 0.1 g Pt/ZrO 2-Im and 2 mmol benzene inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetone, drop into 0.1 g TS-1, Ti-MWW, Ti-Beta, Ti-MCM-41, Ti-SBA-15, Ti-HMS, Fe-ZSM-5, Cu-AlPO more respectively 4-5, Cu-SBA-15, V-SBA-15 molecular sieve or H 4PMo 11VO 40, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature is appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.Benzene transformation efficiency, phenol selectivity and Resorcinol selectivity are seen table 5.
Table 5 embodiment 10 results
Catalyzer Benzene transformation efficiency % Phenol selectivity % Resorcinol selectivity %
TS-1 41 96 4
Ti-MWW 58 92 8
Ti-MCM-41 38 94 6
Ti-SBA-15 39 95 5
Ti-HMS 14 97 3
Fe-ZSM-5 15 93 7
Cu-AlPO 4-5 26 82 18
Cu-SBA-15 21 89 11
V-SBA-15 39 88 12
H 4PMo 11VO 40 53 97 3
Embodiment 11:Weighing 0.1 g Pt/ZrO 2-Im, 0.1 g Ti-MWW molecular sieve and 2 mmol benzene inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetone, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC is respectively 1:9,3:7,1:1,7:3 or 9:1 by carbon monoxide and oxygen pressure ratio and successively feeds carbon monoxide and oxygen, and the control stagnation pressure is 1 MPa, stirs 4 hours, and product is used gas chromatography determination.Benzene transformation efficiency, phenol selectivity and Resorcinol selectivity are seen table 6.
Table 6 embodiment 11 results
Carbon monoxide MPa Oxygen MPa Benzene transformation efficiency % Phenol selectivity % Resorcinol selectivity %
0.1 0.9 11 99 1
0.3 0.7 39 94 6
0.5 0.5 58 92 8
0.7 0.3 50 95 5
0.9 0.1 32 96 4
Embodiment 12:Weighing 0.1 g Pt/ZrO 2-Im, 0.1 g Ti-MWW molecular sieve and 2 mmol benzene inputs fill in the 100mL stainless steel autoclave of 5 mL water and 5 mL acetone, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC is that 1:1 successively feeds carbon monoxide and oxygen by carbon monoxide and oxygen pressure ratio, and the control stagnation pressure is respectively 0.5,1,2 or 3 MPa, stirs 4 hours, and product is used gas chromatography determination.Benzene transformation efficiency, phenol selectivity and Resorcinol selectivity are seen table 7.
Table 7 embodiment 12 results
Stagnation pressure MPa Benzene transformation efficiency % Phenol selectivity % Resorcinol selectivity %
0.5 40 93 7
1 58 92 8
2 64 91 9
3 71 90 10
Embodiment 13:Weighing 0.1 g Pt/ZrO 2-Im, 0.1 g Ti-MWW molecular sieve and 2 mmol toluene inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetone, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.Toluene conversion is 53 %, and the p-methyl phenol selectivity is 98 %.
Embodiment 14:Weighing 0.1 g Pt/ZrO 2-Im, 0.1 g Ti-MWW molecular sieve and 2 mmol methyl-phenoxide inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetone, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.The methyl-phenoxide transformation efficiency is 46 %, and the p methoxy phenol selectivity is 98 %.
Embodiment 15:Weighing 0.1 g Pt/ZrO 2-Im, 0.1 g Ti-MWW molecular sieve and 2 mmol chlorobenzene inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetone, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.The chlorobenzene transformation efficiency is 32 %, and the para-chlorophenol selectivity is 99 %.
Embodiment 16:Weighing 0.1 g Pt/ZrO 2-Im, 0.1 g Ti-MWW molecular sieve and 2 mmol phenylformic acid inputs fill in the 100mL stainless steel autoclave of 5 mL water and 5 mL acetone, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.The phenylformic acid transformation efficiency is 29 %, and the PHB selectivity is 98 %.
Embodiment 17:Weighing 0.1 g Pt/ZrO 2-Im, 0.1 g Ti-MWW molecular sieve and 2 mmol phenol inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetone, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.Phenol conversion is 68 %, and the Resorcinol selectivity is 70 %, selectivity 30 % of pyrocatechol.
Embodiment 18:Weighing 0.1 g Pt/ZrO 2-Im, 0.1 g Ti-MWW molecular sieve and 2 mmol naphthalene inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetone, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.The naphthalene transformation efficiency is 47 %, and the β-Nai Fen selectivity is 64 %, and the naphthyl alcohol selectivity is 36 %.
Embodiment 19:Prepared catalyzer 0.1 g, 0.1 mmol H among the weighing embodiment 1 to embodiment 4 5SW 11VO 40Heteropolyacid and 2 mmol benzene inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetate, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.Benzene transformation efficiency, phenol selectivity and Resorcinol selectivity are seen table 8.
Table 8 embodiment 19 results:
Loaded noble metal catalyst Benzene transformation efficiency % Phenol selectivity % Resorcinol selectivity %
Pt/ZrO 2-Im 36 87 13
Pd/ZrO 2-Im 42 83 17
Rh/ZrO 2-Im 27 89 11
Ru/ZrO 2-Im 30 89 11
Ir/ZrO 2-Im 31 90 10
Ag/ZrO 2-Im 11 93 7
Au/CeO 2-DP 18 94 6
Embodiment 20:Weighing 0.1 g Pd/ZrO 2-Im, 0.1 mmol H 5SMo 11VO 40Heteropolyacid and 2 mmol benzene inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetate, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.The benzene transformation efficiency is 38 %, and the phenol selectivity is 85 %, and the Resorcinol selectivity is 15 %.
Embodiment 21:Weighing 0.1 g Pd/ZrO 2-Im, 0.1 mmol H 5SW 11VO 40Heteropolyacid and 2 mmol naphthalene inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetate, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.The naphthalene transformation efficiency is 39 %, and the β-Nai Fen selectivity is 69 %, and the naphthyl alcohol selectivity is 31 %.
Embodiment 22:Weighing 0.1 g Pd/ZrO 2-Im, 0.1 mmol H 5SW 11VO 40Heteropolyacid and 2 mmol toluene inputs fill in the 100 mL stainless steel autoclaves of 5 mL water and 5 mL acetate, with after the carbon monoxide displacement autoclave air, the autoclave internal temperature are appreciated 80 then oC feeds 0.5 MPa carbon monoxide, and aerating oxygen to stagnation pressure is 1 MPa again, stirs 4 hours, and product is used gas chromatography determination.Toluene conversion is 42 %, and the p-methyl phenol selectivity is 88 %.

Claims (10)

1. the method for the promoted molecular oxygen direct oxidation of a CO hydroxylation aromatic hydroxy compound; It is characterized in that; With the aromatic hydroxy compound is substrate; Use by loaded noble metal catalyst with contain the hetero-atom molecular-sieve of Ti, V, Cu or Fe or the combination catalyst that heteropolyacid salt is formed, be solvent with the mixed solution of water and organic solvent; Feed CO and O 2, CO and O 2Pressing force is than being 0.1:1～9:1, and total pressure is 0.5～3 MPa; Under CO promoted, by molecular oxygen direct oxidation hydroxylation aromatic hydroxy compound, temperature of reaction was 20-150 OC, make the corresponding phenolic compound; Wherein, said substrate and solvent are 0.01:1～0.2:1 by mass ratio.
2. method according to claim 1 is characterized in that, its metal of described loaded noble metal catalyst is selected from one or more among Pt, Pd, Rh, Ru, Ir, Au or the Ag.
3. method according to claim 1 is characterized in that, its carrier of described loaded noble metal catalyst is selected from TiO 2, CeO 2, Fe 2O 3, Al 2O 3And ZrO 2In one or more.
4. according to claim 2 or 3 described methods, it is characterized in that described loaded noble metal catalyst prepares through following method: coprecipitation method, deposition-precipitation method, colloid method or pickling process.
5. method according to claim 1; It is characterized in that; The hetero-atom molecular-sieve of the described Ti of containing, V, Cu or Fe or heteropolyacid salt are selected from the silicon oxide molecular sieve of the MFI, MWW, MCM, HMS, Beta or the SBA configuration that contain Ti, V, Cu or Fe, contain the aluminium phosphate molecular sieve of Cu and contain the tungstate of V or in the molybdate one or more.
6. method according to claim 1 is characterized in that, the mol ratio of noble metal catalyst is 50:1～1000:1 in said substrate and the combination catalyst; In the combination catalyst, the mass ratio of said loaded noble metal catalyst and said hetero-atom molecular-sieve or heteropolyacid salt is 0.5:1～2:1.
7. method according to claim 1 is characterized in that, organic solvent and water are 1:9～9:1 by volume in the mixed solvent.
8. method according to claim 7 is characterized in that described organic solvent is selected from methyl alcohol, acetone, acetonitrile or acetate.
9. method according to claim 1 is characterized in that, described aromatic hydroxy compound is replacement/unsubstituted benzene and replacement/unsubstituted condensed-nuclei aromatics.
10. method according to claim 9 is characterized in that, the substituting group of described substituted benzene and replacement condensed-nuclei aromatics is one or more in alkyl, alkoxyl group, hydroxyl, fluorine, chlorine, bromine, iodine, cyanic acid, acyl group, trifluoromethyl, nitro or the carboxyl.
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CN104549414A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Catalyst for hydroxylating aromatics directly and preparation method of catalyst
CN104549413A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Nanogold catalyst for preparing phenol through direct hydroxylation of benzene as well as preparation method and application of nanogold catalyst
CN110407225A (en) * 2018-04-28 2019-11-05 中国石油化工股份有限公司 One kind Titanium Sieve Molecular Sieve containing noble metal and its synthetic method and application
CN111116320A (en) * 2018-10-30 2020-05-08 中国石油化工股份有限公司 Method for preparing benzenediol by directly hydroxylating phenol

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CN104549414A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Catalyst for hydroxylating aromatics directly and preparation method of catalyst
CN104549413A (en) * 2013-10-28 2015-04-29 中国石油化工股份有限公司 Nanogold catalyst for preparing phenol through direct hydroxylation of benzene as well as preparation method and application of nanogold catalyst
CN104549414B (en) * 2013-10-28 2017-02-08 中国石油化工股份有限公司 Catalyst for hydroxylating aromatics directly and preparation method of catalyst
CN104549413B (en) * 2013-10-28 2017-05-17 中国石油化工股份有限公司 Nanogold catalyst for preparing phenol through direct hydroxylation of benzene as well as preparation method and application of nanogold catalyst
CN110407225A (en) * 2018-04-28 2019-11-05 中国石油化工股份有限公司 One kind Titanium Sieve Molecular Sieve containing noble metal and its synthetic method and application
CN110407225B (en) * 2018-04-28 2021-07-09 中国石油化工股份有限公司 Titanium-silicon molecular sieve containing noble metal and synthesis method and application thereof
CN111116320A (en) * 2018-10-30 2020-05-08 中国石油化工股份有限公司 Method for preparing benzenediol by directly hydroxylating phenol

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