CN104549414A - Catalyst for hydroxylating aromatics directly and preparation method of catalyst - Google Patents
Catalyst for hydroxylating aromatics directly and preparation method of catalyst Download PDFInfo
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Abstract
The invention provides a catalyst for hydroxylating aromatics directly and a preparation method of the catalyst. The catalyst is composed of a supported copper-based catalyst and a Ti, V, Cu or Fe heteroatom-containing zeolite, mixed solution of water and organic solvent is used as solvent, and the aromatics can be directly oxidized and hydroxylated by O2 under the action of CO. The catalyst can be prepared simply, has low price and mild reaction condition and can be used for green oxidation and hydroxylation processes of the aromatics.
Description
Technical field
The invention belongs to chemical catalyst technical field, be specifically related to for the direct hydroxylated Catalysts and its preparation method of aromatic compound.
Background technology
The hydroxylated product of aromatic compound has extremely important at chemical industry and pharmaceutical field and applies widely.At present, aromatic dihydroxylation process is the overwhelming majority undertaken by multistep reaction method, and its process is complicated, high to equipment requirement, unfavorable to production.Phenol is the simplest a kind of phenolic compound, is commonly called as carbolic acid, hydroxy benzenes, is also most important a kind of large Organic Chemicals in aromatic hydrocarbons hydroxylated product, is mainly used in synthesis of bisphenol A, caprolactam, adipic acid and salicylic acid etc.At present, the main production process of phenol is production phenols, and the method experience three-step reaction, major defect is complicated with technique, and energy consumption is high, and serious to equipment corrosion, particularly its accessory substance acetone demand is far below phenol.Therefore, study and be of great significance by the new technology tool of aromatic direct hydroxylation phenolic compound.
Chinese patent CN201010589356.5 provide a kind of with benzene and hydroxylamine salt for raw material, sodium molybdate, ammonium molybdate or Supported molybdenum oxide are catalyst, lower fatty acid or inorganic acid aqueous solution are the benzene direct hydroxylation method of solvent, and the conversion ratio of benzene and phenol yield are respectively 20-76 % and 30-75 %.It is carrier with coal mass active carbon that CN201010543037.0 gives a kind of, by the benzene hydroxylation method of infusion process load ferric sulfate as catalyst, with H
2o
2for oxidant 30
oreact 8 h under C, phenol yield can reach 22.5 %.In addition, document (D. Meloni, R. Monaci, V. Solinas, et al, J. Catal., 314(2003): 169-178) with Fe-MFI molecular sieve for catalyst, N
2o is oxidant, gas-phase reaction synthesizing phenol, and reaction temperature is 400
ounder C, the conversion ratio of benzene and phenol selectivity are respectively 20 % and 90 %.Said method is compared with conventional method, although simplify technique, main deficiency is azanol, H
2o
2and N
2o price costly, has greater environmental impacts, and not high based on the phenol selectivity of oxidant.
Be that to realize phenyl ring direct hydroxylation be target in industrial quarters and academic research to oxidant with molecular oxygen all the time, be considered to the large challenging problem of most of catalytic field ten.The method that it is catalyst that research mainly concentrates on molybdenum, tungsten, copper or vanadium-based materials, document (H. Yamanaka, R. Hamada, H. Nibuta, et al, J. Mol. Catal. A:Chemical, 178(2002): take 89-95) Cu/ZSM-5 as the phenol yield of catalyst gained be 1.5%; 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 catalyst, liquid-phase oxidation benzene synthesizing phenol, the conversion ratio of benzene and the selective of phenol are respectively 9.2% and 91.8%.When taking molecular oxygen as oxidant, although it is cheap, the conversion ratio of benzene is lower, is usually no more than 20 %.For taking molecular oxygen as oxidant, the problem low to benzene oxidatoin ability, document (S. Niwa, M. Eswaramoorthy, J. Nair, et al, Science, 295(2002): 105-107) with palladium film for catalyst, oxygen is oxygen source, and hydrogen is auxiliary agent, and benzene feedstock can be converted into phenol in fixed bed reactors, but the conversion ratio of benzene is not high, and hydrogen Pyrogentisinic Acid's is selective lower.Simultaneously, document (S.L. Shu, Y. Huang, X.J. Hu, J. Phys. Chem. C, 113(2009): 19618-19622) think through repeatedly testing, above-mentioned palladium film catalyst there is no the performance of catalysis benzene direct hydroxylation under the reaction conditions, and very easily causes the damage of film catalyst structure at the hydrogen of catalyst surface generation and the combustion reaction of oxygen.In addition, CN20100521323.7 disclose with containing the heteropolyacid salt of vanadium or molecular sieve for catalyst, O
2for the benzene hydroxylation method of oxidant, under the organic molecule with hydrogen migration ability promotes, the highest yield of phenol is 14 %, and it is 2,2 that these hydrogen migration organic compounds comprise, 6,6-tetramethyl piperidine free radical (TEMPO), 4-amino-TEMPO, 4-hydroxyl-TEMPO, NHPI etc., price is more expensive.By above-mentioned current as seen take molecular oxygen as the benzene direct hydroxylation method of oxidant, its benzene low conversion rate, phenol yield is low, and ability reused by catalyst, and reaction promoter is expensive, and application prospect remains to be discussed.
For taking molecular oxygen as oxidant, the problem low to benzene oxidatoin ability, patent CN 102850154 A discloses a kind of catalyst containing noble metal, metal oxide and HTS three kinds of components, is that oxidant can by benzene direct hydroxylation to phenol under carbon monoxide promotes with oxygen.Although the reaction condition gentleness that the method is used, phenol yield is higher, and the active component in catalyst is noble metal, and price is very expensive.
Summary of the invention
Technical problem to be solved by this invention is the problem of existing catalyst high cost, provide a kind of newly for the direct hydroxylated catalyst of aromatic compound.This catalyst preparing is simple, low in raw material price, has good catalytic activity for preparing phenol by directly hydrocylating benzene reaction.
In order to solve the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of for the direct hydroxylated catalyst of aromatic compound, catalyst comprises catalyst I and II, and catalyst I is carried copper sill, comprises following component with weight parts:
A) copper of 5 ~ 60 parts;
B) metal oxide carrier of 40 ~ 95 parts, metal oxide carrier is selected from ZnO, Al
2o
3, ZrO
2and CeO
2in one or more;
Catalyst II is hetero-atom molecular-sieve, comprises following component with weight parts:
A) at least one element be selected from titanium, vanadium of 0.1 ~ 10 part;
B) molecular sieve of 90 ~ 99.9 parts, molecular screening is from the SiO of MFI, MWW, MCM, HMS, Beta or SBA configuration
2one in molecular sieve;
The weight ratio of described catalyst I and catalyst II is 1:9 ~ 9:1.
In technique scheme, with catalyst I weight parts, in carried copper sill, the preferred content of copper is 20 ~ 50 parts; With catalyst II weight parts, the content being selected from least one element in titanium, vanadium is 0.3 ~ 2 part; Hetero-atom molecular-sieve is selected from the SiO of MWW configuration
2molecular sieve; The preferred weight ratio of catalyst I and catalyst I I is 1.5:1 ~ 2:1.
In technique scheme, the preferred version of preparing of carried copper sill is gel oxalate precipitation method, comprises the following steps:
1) copper nitrate and zinc nitrate, aluminum nitrate, zirconium nitrate or cerous nitrate are dissolved in ethanol, are mixed with the solution I that metal ion total concentration is 0.05 ~ 0.5mol/L;
2) take oxalic acid according to 1.2 times of mole total amount of metal ion in solution I and be dissolved in ethanol, being mixed with the solution II that concentration is identical with solution I;
3) under agitation, solution II is injected solution I fast, obtain colloidal sol.Gained colloidal sol is filtered, washing, dry, 0.5 ~ 2
o300 ~ 400 are warming up under the speed of C/min
oc roasting 4 h.
In technique scheme, step 2) in metal ion mole total amount be total amount of substance of metal ion.
The using method of catalyst provided by the present invention in the direct hydroxylating of aromatic hydrocarbons is: be 60 ~ 90 in reaction temperature
oc, CO and O
2stagnation pressure be 0.5 ~ 5 MPa, pressure ratio is under the condition of 0.1:1 ~ 9:1, and be that the arene solution of 1 ~ 10 % and catalyst exposure react and produce hydroxylation product by mass concentration, wherein, in mixed solution, organic solvent and water are 1:9 ~ 9:1 by volume; Organic solvent is selected from methyl alcohol, acetone, acetonitrile or acetic acid.
In the present invention, described aromatic compound is replacement/unsubstituted benzene and replacement/unsubstituted condensed-nuclei aromatics.Described substituting group is one or more in alkyl, alkoxyl, hydroxyl, fluorine, chlorine, bromine, iodine, cyano group, acyl group, trifluoromethyl, nitro or carboxyl.
Copper particle size in the copper-based material adopting gel oxalate precipitation method to obtain is less, be more evenly distributed, very favourable to catalytic activity, it is suitable according to the technology of the catalytic effect and existing use noble metal catalyst that are used for aromatic compound direct hydroxylating gained after suitable weight ratio mechanical mixture with hetero-atom molecular-sieve, and wherein target product is selective also higher.Simultaneously when the weight ratio of catalyst I and catalyst II is 1.5:1 ~ 2:1, when catalyst weight is identical, its hydroxylation activity of catalyst comparing other weight ratios is significantly improved, the conversion ratio of benzene can reach more than 60%, achieve unforeseeable technique effect, because the price of copper is far below noble metal, therefore catalyst provided by the invention has more using value at the direct hydroxylating of aromatic hydrocarbons.
Below by embodiment in detail the present invention is described in detail, but content of the present invention is not limited thereto.
Detailed description of the invention
[embodiment 1]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 15 g zirconium nitrates to be dissolved in ethanol, then add 4.14 g copper nitrates according to final copper content 20 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 1
oc/min rises to 350
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst A.
Weigh catalyst A 0.27 g 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 2]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 15 g zirconium nitrates to be dissolved in ethanol, then add 7.1g copper nitrate according to final copper content 30 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 1
oc/min rises to 350
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst B.
Weigh catalyst B 0.27 g respectively 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 3]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 15 g zirconium nitrates to be dissolved in ethanol, then add 11.02 g copper nitrates according to final copper content 40 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 1
oc/min rises to 350
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst C.
Weigh catalyst C 0.27 g respectively 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 4]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 15 g zirconium nitrates to be dissolved in ethanol, then add 16.55 g copper nitrates according to final copper content 50 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 1
oc/min rises to 350
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst D.
Weigh catalyst D 0.27 g 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 5]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 15 g zinc nitrates to be dissolved in ethanol, then add 7.1 g copper nitrates according to final copper content 30 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 1
oc/min rises to 350
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst E.
Weigh catalyst E 0.27 g 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 6]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 115g aluminum nitrate to be dissolved in ethanol, then add 2.66 g copper nitrates according to final copper content 30 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 1
oc/min rises to 350
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst F.
Weigh catalyst F 0.27 g 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 7]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 15g cerous nitrate to be dissolved in ethanol, then add 5.37 g copper nitrates according to final copper content 30 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 1
oc/min rises to 350
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst G.
Weigh catalyst G 0.27 g 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 8]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 15 g zirconium nitrates to be respectively dissolved in ethanol, then add 7.1g copper nitrate according to final copper content 30 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 0.5
oc/min rises to 350
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst H.
Weigh catalyst H 0.27 g 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 9]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 15 g zirconium nitrates to be respectively dissolved in ethanol, then add 7.1g copper nitrate according to final copper content 30 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 1.5
oc/min rises to 350
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst I.
Weigh catalyst I 0.27 g 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 10]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 15 g zirconium nitrates to be respectively dissolved in ethanol, then add 7.1g copper nitrate according to final copper content 30 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 2
oc/min rises to 350
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst J.
Weigh catalyst J 0.27 g 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 11]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 15 g zirconium nitrates to be respectively dissolved in ethanol, then add 7.1g copper nitrate according to final copper content 30 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 1
oc/min rises to 300
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst K.
Weigh catalyst K 0.27 g 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 12]
Under room temperature, piperidinyl-1 82.5 g is dissolved in 513 g water, above-mentioned solution is divided into two parts, a part joins 10.8 g butyl titanate stirring at room temperature with vigorous stirring and is hydrolyzed 0.5 h, adds 124.2 g boric acid stirring at room temperature dissolve 0.5 h at another part.90 g Ludox are divided into two parts to be joined in the solution of above-mentioned titanium and boron respectively, continues stirring 2 h, is mixed by above-mentioned two kinds of solution and continue to stir l h to make its plastic.Above-mentioned gel is transferred in 2 L stainless steel cauldrons of band teflon lined, 170
ocrystallization 5 days under C, the gained presoma nitric acid of 2 mol/L washs to remove the boron in skeleton, then 550
ounder C, roasting 10 h obtains Ti-MWW.
First take 15 g zirconium nitrates to be respectively dissolved in ethanol, then add 7.1g copper nitrate according to final copper content 30 %, be mixed with the solution of total concentration 0.5 mol/L.The dissolving oxalic acid taking the total amount of substance of metal ion 1.2 times again, in ethanol, is mixed with the solution of total concentration 0.5 mol/L equally.Under intense agitation, oxalic acid solution is joined fast in copper, zirconium solution, form precipitation.By sedimentation and filtration, with 2 L distilled water washings, 110
odrying 12 hours under C, more in atmosphere with 1
oc/min rises to 400
oc roasting 4 hours.After cooling, obtained copper-based material, is expressed as catalyst L.
Weigh catalyst L 0.27 g 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 13]
TEOS:TPAOH in molar ratio: butyl titanate: H
2o=l:0.1:0.033:10, preparation reaction mixture solution, mixes with 5 gTEOS by rare TPAOH solution, is slowly added by butyl titanate with vigorous stirring, be stirred into the reactant mixture of low organic base template concentration, wherein TPAOH concentration is 5 wt%.By the reactant mixture that obtains in 60
othe plastic that is hydrolyzed under C condition 1 h.Then 80 are warming up to
oc, catches up with alcohol to concentrate 3 h, obtains the reactant mixture colloidal sol clear liquid of high organic base template concentrations, and extremely wherein TPAOH concentration is 25 wt%.Reactant mixture colloidal sol clear liquid is transferred in autoclave, in 170
oc dynamic crystallization 2 days, the good reactant mixture of crystallization after filtration, washing, 80
oc drying, 550
otS-1 molecular sieve is obtained after C roasting 4 h.
Weigh catalyst B 0.27 g obtained in embodiment 2 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add TS-1 molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
[embodiment 14]
By H type modenite in atmosphere 500
oafter C roasting 4 h, to reflux dealuminzation with nitric acid.Get the modenite of 2 g through the dealuminzation of 773 K process 4 h, with the TiCl of helium flow dilution
4steam (1.7 KPa) at 773 K process 1 h, then sample again with pure helium 773 K process l h to remove unreacted TiCl
4, then cool to room temperature.Through TiCl
4the sample of process spends deionized water, then namely obtains Ti-MOR at dry 24 h of 383 K.
Weigh catalyst B 0.27 g obtained in embodiment 2 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MOR molecular sieve 0.13 g and 2 mmol benzene, then with air in carbon monoxide displacement autoclave, autoclave temperature is risen to 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 1.
Table 1
[embodiment 15]
Weigh catalyst B obtained in a certain amount of embodiment 2 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol, then add Ti-MWW obtained in 2 mmol benzene and a certain amount of embodiment 1, then with air in carbon monoxide displacement autoclave, autoclave temperature is appreciated 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Benzene conversion ratio, phenol selectivity are in table 2.
Table 2
[embodiment 16]
Weigh catalyst B 0.27 g obtained in embodiment 2 350
oc 10 %H
2/ N
2add rapidly after middle reductase 12 h and fill in 100 mL stainless steel autoclaves of water and acetone, add Ti-MWW obtained in benzene and 0.13 g embodiment 1 again, then with after air in carbon monoxide displacement autoclave, autoclave temperature is risen to assigned temperature, successively pass into carbon monoxide and oxygen again to specified pressure, stir 4 hours, product gas chromatography determination.Benzene conversion ratio and phenol selectivity are in table 3.
Table 3
[embodiment 17]
First catalyst D 0.27 g of weighing prepared by embodiment 4 is 350
oc 10 %H
2/ N
2add rapidly in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol after middle reductase 12 h, add Ti-MWW molecular sieve 0.13 g prepared in embodiment 1 and 2 mmol toluene again, then with air in carbon monoxide displacement autoclave, autoclave temperature is appreciated 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Toluene conversion is 60 %, and p-methyl phenol is selective is 94 %.
[embodiment 18]
First catalyst D 0.27 g of weighing prepared by embodiment 4 is 350
oc 10 %H
2/ N
2add rapidly in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol after middle reductase 12 h, add Ti-MWW molecular sieve 0.13 g prepared in embodiment 1 and 2 mmol methyl phenyl ethers anisoles again, then with air in carbon monoxide displacement autoclave, autoclave temperature is appreciated 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Methyl phenyl ethers anisole conversion ratio is 48 %, and p methoxy phenol is selective is 96 %.
[embodiment 19]
First catalyst D 0.27 g of weighing prepared by embodiment 4 is 350
oc 10 %H
2/ N
2add rapidly in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol after middle reductase 12 h, add Ti-MWW molecular sieve 0.13 g prepared in embodiment 1 and 2 mmol chlorobenzenes again, then with air in carbon monoxide displacement autoclave, autoclave temperature is appreciated 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Chlorobenzene transformation ratio is 31 %, and parachlorophenol is selective is 98 %.
[embodiment 20]
First catalyst D 0.27 g of weighing prepared by embodiment 4 is 350
oc 10 %H
2/ N
2add rapidly in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol after middle reductase 12 h, add Ti-MWW molecular sieve 0.13 g prepared in embodiment 1 and 2 mmol benzoic acid again, then with air in carbon monoxide displacement autoclave, autoclave temperature is appreciated 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Conversion of benzoic acid is 23 %, and P-hydroxybenzoic acid is selective is 98 %.
[embodiment 21]
First catalyst D 0.27 g of weighing prepared by embodiment 4 is 350
oc 10 %H
2/ N
2add rapidly in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol after middle reductase 12 h, add Ti-MWW molecular sieve 0.13 g prepared in embodiment 1 and 2 mmol phenol again, then with air in carbon monoxide displacement autoclave, autoclave temperature is appreciated 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Phenol conversion is 64 %, and hydroquinones is selective is 71 %, selective 29 % of catechol.
[embodiment 22]
First catalyst D 0.27 g of weighing prepared by embodiment 4 is 350
oc 10 %H
2/ N
2add rapidly in the 100 mL stainless steel autoclaves filling 5 mL water and 5 mL methyl alcohol after middle reductase 12 h, add Ti-MWW molecular sieve 0.13 g prepared in embodiment 1 and 2 mmol naphthalenes again, then with air in carbon monoxide displacement autoclave, autoclave temperature is appreciated 80
oc, passes into 1.5 MPa carbon monoxide, then to pass into oxygen to stagnation pressure be 3 MPa, stirs 4 hours, product gas chromatography determination.Naphthalene conversion ratio is 50 %, and betanaphthol is selective is 65 %, and alpha-Naphthol is selective is 35 %.
Claims (9)
1. for the direct hydroxylated catalyst of aromatic compound, catalyst comprises catalyst I and II, and catalyst I is carried copper sill, comprises following component with weight parts:
A) copper of 5 ~ 60 parts;
B) metal oxide carrier of 40 ~ 95 parts, metal oxide carrier is selected from ZnO, Al
2o
3, ZrO
2and CeO
2in one or more;
Catalyst II is hetero-atom molecular-sieve, comprises following component with weight parts:
A) at least one element be selected from titanium, vanadium of 0.1 ~ 10 part;
B) molecular sieve of 90 ~ 99.9 parts, molecular screening is from the SiO of MFI, MWW, MCM, HMS, Beta or SBA configuration
2one in molecular sieve;
The weight ratio of described catalyst I and catalyst II is 1:9 ~ 9:1.
2. according to claim 1 for the direct hydroxylated catalyst of aromatic compound, it is characterized in that described catalyst I is standby by gel oxalate precipitation legal system, comprise the following steps:
1) copper nitrate and zinc nitrate, aluminum nitrate, zirconium nitrate or cerous nitrate are dissolved in ethanol, are mixed with the solution I that metal ion total concentration is 0.05 ~ 0.5 mol/L;
2) take oxalic acid according to 1.2 times of mole total amount of metal ion in solution I and be dissolved in ethanol, being mixed with the solution II that concentration is identical with solution I;
3) under agitation, solution II is injected solution I fast, obtains colloidal sol, gained colloidal sol is filtered, washing, dry, 0.5 ~ 2
o300 ~ 400 are warming up under the speed of C/min
oc roasting 4 h obtains catalyst.
3. according to claim 1 for the direct hydroxylated catalyst of aromatic compound, it is characterized in that with catalyst I weight parts, the content of copper is 20 ~ 50 parts.
4. according to claim 1ly it is characterized in that with catalyst II weight parts for the direct hydroxylated catalyst of aromatic compound, the content being selected from least one element in titanium, vanadium is 0.3 ~ 2 part.
5. according to claim 1 for the direct hydroxylated catalyst of aromatic compound, it is characterized in that described hetero-atom molecular-sieve is selected from the SiO of MWW configuration
2molecular sieve.
6. according to claim 1 for the direct hydroxylated catalyst of aromatic compound, it is characterized in that the weight ratio of catalyst I and catalyst II is 1.5:1 ~ 2:1.
7. the direct hydroxylating phenol of aromatic compound a method, with aromatic compound, CO and O
2for raw material, with the mixed liquor of water and organic solvent for solvent, the mass concentration of aromatic compound is 1 ~ 10 %, and the mixed solvent volume ratio of organic solvent and water is 1:9 ~ 9:1; Organic solvent is selected from methyl alcohol, acetone, acetonitrile or acetic acid; Be 60-90 in reaction temperature
oc; Stagnation pressure is 0.5-5 MPa, wherein CO and O
2pressure ratio be under the condition of 0.1:1 ~ 9:1, under the effect of catalyst described in any one of claim 1 ~ 7, be obtained by reacting phenol.
8. method according to claim 8, is characterized in that described aromatic compound is replacement/unsubstituted benzene and replacement/unsubstituted condensed-nuclei aromatics.
9. method according to claim 8, is characterized in that described substituted benzene and the substituting group replacing condensed-nuclei aromatics are one or more in alkyl, alkoxyl, hydroxyl, fluorine, chlorine, bromine, iodine, cyano group, acyl group, trifluoromethyl, nitro or carboxyl.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109437224A (en) * | 2018-11-16 | 2019-03-08 | 湖北大学 | A kind of synthetic method of the cavity of micron containing hetero atom reaction type HBMZ zeolite molecular sieve |
| 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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| US6191318B1 (en) * | 1998-06-15 | 2001-02-20 | Korea Research Institute Of Chemical Technology | Process for preparing hydroxylated aromatics by hydrogen and oxygen |
| CN1559682A (en) * | 2004-03-05 | 2005-01-05 | 华东师范大学 | Bitransition metal modified molecular sieve and its preparation and use |
| CN102731234A (en) * | 2012-07-05 | 2012-10-17 | 复旦大学 | CO (carbon monoxide)-promoted method for directly oxygenizing hydroxylated aromatic compound by molecular oxygen |
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| US6191318B1 (en) * | 1998-06-15 | 2001-02-20 | Korea Research Institute Of Chemical Technology | Process for preparing hydroxylated aromatics by hydrogen and oxygen |
| CN1559682A (en) * | 2004-03-05 | 2005-01-05 | 华东师范大学 | Bitransition metal modified molecular sieve and its preparation and use |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| CN109437224A (en) * | 2018-11-16 | 2019-03-08 | 湖北大学 | A kind of synthetic method of the cavity of micron containing hetero atom reaction type HBMZ zeolite molecular sieve |
| CN109437224B (en) * | 2018-11-16 | 2021-08-31 | 湖北大学 | Synthesis method of heteroatom-containing micron cavity reactor type HBMZ zeolite molecular sieve |
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