CN101147870A - Catalyst for synthesizing diphenyl carbonate used in non-homogeneuos oxidation carbonylation and method for preparing the same - Google Patents
Catalyst for synthesizing diphenyl carbonate used in non-homogeneuos oxidation carbonylation and method for preparing the same Download PDFInfo
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- CN101147870A CN101147870A CNA2007100537806A CN200710053780A CN101147870A CN 101147870 A CN101147870 A CN 101147870A CN A2007100537806 A CNA2007100537806 A CN A2007100537806A CN 200710053780 A CN200710053780 A CN 200710053780A CN 101147870 A CN101147870 A CN 101147870A
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Abstract
The present invention relates to a catalyst for synthesizing diphenyl carbonate by utilizing heterogeneous oxidation carbonylation and preparation method of said catalyst. Said preparation method includes the following steps: making palladium salt be loaded on the manganese series composite metal oxide carrier, said manganese series composite metal oxide carrier is formed from manganese oxygen compound and metal oxide of any one kind or more than one kind of La, Ce, Ti, Zr, V, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Zn, Bi, Pb and Sn, the loaded quantity of active component Pd is 0.01wt%-10wt%, utilizing impregnating process, precipitation process or mixed fuel burning process to make the active component palladium salt be loaded on the manganese series composite metal oxide carrier, drying and calcining for 1-8h at 200-600deg.C so as to obtain the invented solid catalyst. Said catalyst can be used for preparing diphenyl carbonate, its productivity is up to 22.0% and its selectivity is up to 98.3%.
Description
Technical field
The present invention relates to a kind of catalyst and Preparation of catalysts method of heterogeneous oxidative carbonylation diphenyl carbonate synthesis.
Background technology
Merlon (PC) is unique product with transparency in the five big general engineering plastic, also is the fastest general engineering plastic of growth in recent years, and it has a wide range of applications in fields such as machine-building, electronics, military affairs, safety, optical-fibre communications industries.The production method of PC mainly contains the melt transesterification process of phosgene interface polycondensation and non-phosgene, thereby the former is owing to use a large amount of hypertoxic phosgene to cause environmental pollution; The latter is good and receive much concern to environment.
Diphenyl carbonate (DPC) is one of raw material of the synthetic PC of melt transesterification process, and its synthetic method mainly contains: phosgenation, ester-interchange method and phenol oxidation carbonylation method.The synthetic DPC of phosgenation is because of the severe toxicity of raw material phosgene, and byproduct hydrochloric acid is serious to equipment corrosion in the reaction, contaminated environment, so this method just progressively is eliminated.Ester-interchange method is to be raw material with dimethyl carbonate and phenol, and through the synthetic DPC of two step ester exchanges, this method cost of material height, reaction is subjected to thermodynamic (al) restriction, reaction rate is slow, productive rate is low, process route is long, the product separation is difficult.The oxidative carbonylation method is to utilize CO, O
2With phenol be raw material next step synthetic DPC of effect at catalyst, compare preceding two kinds of technologies, the oxidative carbonylation method has that technology is simple, the cheap facility of raw material, atom utilization height, water is unique side product and advantage such as pollution-free in theory, is the most promising DPC green synthesis process.At present, the catalyst of the synthetic DPC of domestic and international application oxidative carbonylation method mostly is a liquid-phase catalyst, and its shortcoming is the catalyst recovery difficulty, and selectivity and yield are all lower.
Summary of the invention
The objective of the invention is deficiency, and a kind of heterogeneous oxidative carbonylation diphenyl carbonate synthesis method and this method catalyst system therefor and method for preparing catalyst are provided at above-mentioned prior art existence.The present invention has not only simplified the follow-up separation process of diphenyl carbonate product, and catalyst helps suitability for industrialized production to the selectivity and the yield height of diphenyl carbonate.
Heterogeneous oxidative carbonylation diphenyl carbonate synthesis method catalyst system therefor is: the manganese that periodic table of elements group VIII Pd salt is carried on as carrier is composite metal oxide, wherein carrier manganese be composite metal oxide by among manganese and oxygen compound and La, Ce, Ti, Zr, V, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Zn, Bi, Pb, the Sn any more than a kind or a kind metal oxide formed, the load capacity of active component Pd is 0.01%-10.0% (wt), and its suitable load capacity is: 0.10%-1.0%.
The parent that above-mentioned formation manganese is the composite metal oxide carrier is oxide, halide, acetate, carbonate, sulfate, the nitrate of Mn, La, Ce, Ti, Zr, V, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Zn, Bi, Pb, Sn; Specifically: MnCl
2, Mn (OAc)
2, MnCO
3, MnSO
4, Mn (NO
3)
2, La (NO
3)
3, CeO
2, Ce (OAc)
3, Ce (NO
3)
3, TiCl
4, ZrO
2, ZrCl
4, ZrOCl
2, ZrOCO
3, ZrOSO
4, Zr (AC)
4, V
2O
5, VOCl
2, NaVO
3, NaVO
3, NH
4VO
3, VOSO
4, Cr (NO
3)
3, MoO
3, (NH
4)
2MoO
4, Na
2MoO
4, Na
2WO
4, FeCl
3, Fe
2(SO
4)
3, Fe (NO
3)
3, CoO, CoCl
2, Co (OAc)
2, CoSO
4, NiO, Ni (OAc)
2, NiSO
4, Cu
2O, CuO, CuF, CuCl, CuBr, CuI, CuSO
4, CuBr
2, CuCl
2, Cu (OAc)
2, Cu
2(OH)
2CO
3, AgNO
3, ZnCl
2, ZnSO
4, BiO, Bi
2O
3, BiCl
2, BiCl
3, BiSO
4, Bi
2(SO
4)
3, PbO, Pb
3O
4, PbCl
2, Pb (OAc)
2, PbCO
3, Pb
2(OH)
2CO
3, PbSO
4, SnO
2, SnCl
2, SnCl
4
Manganese is that the preparation method of composite metal oxide carrier has coprecipitation or mechanical milling method.
Coprecipitation is: choose MnO, MnCl from the above-mentioned parent that is used for preparing carriers
2, Mn (OAc)
2, MnCO
3, MnSO
4Or Mn (NO
3)
2Any salt solution mix of metal more than a kind or a kind among solution and La, Ce, Ti, Zr, V, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Zn, Bi, Pb, the Sn, MnO, MnCl
2, Mn (OAc)
2, MnCO
3, MnSO
4Or Mn (NO
3)
2Solution is any ratio with the mol ratio of each selected salting liquid, and with alkali solution precipitate, aging 10-24 hour, filters then, with the gained sediment in vacuum drying chamber in 90～120 ℃ of dryings 2～24 hours; Again with dry thing in Muffle furnace in 200～1000 ℃ of following roastings 2～12 hours, promptly getting manganese is the composite metal oxide carrier.
Described mechanical milling method is divided into direct method and indirect method.
The direct mechanical polishing is: choose any oxide, nitrate or carbonate mixing and stirring on grinder of metal more than a kind or a kind among the carbonate of Mn or nitrate and La, Ce, Ti, Zr, V, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Zn, Bi, Pb, the Sn from the above-mentioned parent that is used for preparing carriers; MnCO
3Or Mn (NO
3)
2With the mol ratio of each selected metallic compound be any ratio, with mixture in vacuum drying chamber in 90～120 ℃ of dryings 2～24 hours; Again with dry thing in Muffle furnace in 200～1000 ℃ of following roastings 2～12 hours, promptly getting manganese is the composite metal oxide carrier.
Mechanical milling method is indirectly: choose manganese salt solution alkali precipitation, aging 10-24 hour, filtration from the above-mentioned parent that is used for preparing carriers, the manganese and oxygen compound presoma, then with manganese and oxygen compound presoma, manganese carbonate or manganese nitrate in vacuum drying chamber dry 2～24 hours; Again with dry thing in Muffle furnace in 200～1000 ℃ of following roastings 2～12 hours, manganese and oxygen compound; Again with any oxide, nitrate or carbonate mixing and stirring on grinder of metal more than a kind or a kind among manganese and oxygen compound and the La, the Ce that choose from the above-mentioned parent that is used for preparing carriers, Ti, Zr, V, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Zn, Bi, Pb, the Sn, the mol ratio of manganese and oxygen compound and the metallic compound of respectively selecting for use for arbitrarily than; With mixture in vacuum drying chamber in 90～120 ℃ of dryings 2～24 hours; Again with dry thing in Muffle furnace in 200～1000 ℃ of following roastings 2～12 hours, promptly getting manganese is the composite metal oxide carrier.
Above-mentioned manganese is that the used alkali of composite metal oxide preparing carriers is any one in ammonium carbonate, carbonic hydroammonium, ammoniacal liquor, alkali-metal hydroxide, alkali-metal carbonate, alkali-metal bicarbonate and the urea.Manganese is that drying time, sintering temperature and roasting time preferable in the composite metal oxide preparing carriers process was respectively 8-12 hour, 300～700 ℃ and 4-8 hour.
Above-mentioned Preparation of catalysts method is: the manganese that active substance palladium salt is loaded to by the method for preparing gained is on the O composite metallic oxide catalyst carrier, and drying at 200～600 ℃ of following roasting 1-8 hours, promptly gets required solid catalyst again.Wherein the mode of loading of active material specifically can be: infusion process, the precipitation method or multifuel combustion method; Behind the carrying active substance, the preferable sintering temperature of catalyst and roasting time are respectively 200～500 ℃ and 2-6 hour.
In the above-mentioned Preparation of catalysts, the active substance palladium salt of selecting for use is PdCl
2, Pd (AcO)
2, NaPdCl
4, K
2PdCl
4, (NH
4)
4PdCl
4, (NH
4)
2PdCl
6, (Nbu
4)
2PdCl
4In any one.
Infusion process in the above-mentioned method for preparing catalyst is: with the manganese that makes is that composite metal oxide carrier concentration is 0.001mol/L-1mol/L active substance palladium salt solution impregnation, filter then, drying, got final product at 200-500 ℃ of following roasting 2-6 hour at last, palladium salt used in the method is generally PdCl
2, Pd (AcO)
2, NaPdCl
4
The precipitation method in the above-mentioned method for preparing catalyst are: with the manganese that makes is that composite metal oxide carrier concentration is 0.001mol/L-1mol/L active substance palladium salt solution impregnation, drip an amount of precipitating reagent while stirring, the pH that keeps solution is at 8-9, active component is deposited on the carrier, filter then, wash, drying, got final product at 200-500 ℃ of following roasting 2-6 hour at last.Used precipitating reagent is an inorganic base, specifically can be NaOH, KOH, NH
3H
2O, NH
4HCO
3In any one.
Multifuel combustion method in the above-mentioned method for preparing catalyst is: with active substance palladium salt and manganese is that the composite metal oxide carrier is 0.02-16.5 by weight: 100 mix, and get final product at 200-500 ℃ of following roasting 2-6 hour.
Heterogeneous oxidative carbonylation diphenyl carbonate synthesis method: with CO, O
2, catalyst and phenol, TBAB, benzoquinones add in the autoclave O
2With the mol ratio of CO be 1%～7%, following consumption by weight, catalyst amount 0.5-5 part, 50 parts of phenol, 1 part of TBAB, 74 parts of benzoquinones, 60～120 ℃ of reaction temperatures, reaction pressure are 3-6MPa, react 1-12 hour, catalyst is to the productive rate and the selectivity best result Bie Keda 22.0% and 98.3% of diphenyl carbonate in this synthetic method, and catalyst system therefor is that the active substance palladium salt load manganese that said method makes is the composite metal oxide carrier.
The present invention is as follows than the advantage of prior art:
(1) catalytic activity height.Of the present invention is that composite metal oxide is that the catalyst system and catalyzing of carrier has good catalytic activity to oxidation carbonylation with manganese, consumption at palladium is 0.5% o'clock, the yield of diphenyl carbonate can reach 22%, is better than general heterogeneous catalyst, and catalyst is originally as the hypotoxicity material.
(2) environmentally safe and can etching apparatus.The used solid-phase catalyst of the present invention can etching apparatus and contaminated environment except that low toxicity own yet.
(3) easy regeneration, good stability.The O composite metallic oxide catalyst that the present invention is used can be reused repeatedly, only needs simple roasting can recover activity of such catalysts
(4) preparation is simple, cost is low.The used catalyst preparation process of the present invention is simple and convenient, and raw material is cheap and easy to get, greatly reduces production cost.
The specific embodiment
About method of the present invention, be illustrated with following example, but the present invention never is subjected to the restriction of these examples.
Embodiment 1
Adopt coprecipitation to prepare the Mn-Cu bimetallic oxide: to get 4.1g MnSO
4H
2O adds the 15ml deionized water dissolving, is mixed with solution; Other gets 0.9g CuSO
4, add the 15ml deionized water, wiring solution-forming; Two kinds of solution are mixed, add 4ml concentration and be 20% aqueous sodium carbonate and precipitate, the stirring that does not stop is agingly filtered after 24 hours, then with the gained sediment in vacuum drying chamber in 100 ℃ of dryings 12 hours; Again with dry thing in Muffle furnace in 600 ℃ of following roastings 7 hours, promptly make manganese system complex oxide carrier;
Get PdCl
240mg is dissolved in the 40ml deionized water, with concentrated hydrochloric acid its pH value of solution value is transferred to about 1 heating for dissolving; The above-mentioned manganese system complex oxide carrier that makes is added in the solution, and regulating the pH value with NaOH solution is 8, precipitates active component, and ceaselessly stirred 2 hours, filtration, drying obtained final catalyst in 3 hours 400 ℃ of following roastings at last then, and the load capacity of palladium is 0.7%;
Get the above-mentioned catalyst that makes of 2.0g, 50g phenol, 1g TBAB, 74mg benzoquinones respectively and join in the autoclave of 250ml, feed O
2Pressure be 0.3MPa, the pressure of CO is 4.7MPa, reaction temperature is 60 ℃, reaction pressure is 5MPa, the reaction time is 5 hours, reactant liquor separates by SE-54 type capillary column in gas-chromatography, adopts hydrogen flame detector to carry out check and analysis.Analysis condition is: 250 ℃ of column temperatures, and 250 ℃ of Sample Room temperature, 200 ℃ of detector temperatures, carrier gas is a nitrogen, flow is 1.2ml/min.The employing external standard method is carried out quantitative analysis to the content of diphenyl carbonate, and the yield that gets diphenyl carbonate is 22.0%, and catalyst is 98.3% to the selectivity of diphenyl carbonate.
Embodiment 2
Adopt indirect mechanical milling method to prepare the Mn-Ce bimetallic oxide, get 4.2g MnSO
4H
2O adds the 15ml deionized water dissolving, is mixed with solution; Add 4ml concentration and be 20% aqueous sodium carbonate precipitate, and aging 10 hours, filter, the manganese carbonate presoma; Then with manganese carbonate presoma in vacuum drying chamber dry 12 hours; Again with dry thing in Muffle furnace in 600 ℃ of following roastings 7 hours, Mn oxide; Other gets 0.8g CeO
2, with two kinds of oxides mixing and stirring on grinder, with mixture in vacuum drying chamber in 100 ℃ of dryings 12 hours; Again with dry thing in Muffle furnace in 500 ℃ of following roastings 8 hours, promptly make manganese system complex oxide catalyst carrier;
Get PdCl
240mg is dissolved in the 40ml deionized water, with concentrated hydrochloric acid its pH value of solution value is transferred to about 1, heating for dissolving again, above-mentioned manganese system complex oxide catalyst carrier is added in the solution, and adding NaOH aqueous slkali adjusting pH value then is 8, precipitates active component, and ceaselessly stirred 4 hours, filtration, drying obtained final catalyst in 4 hours 300 ℃ of following roastings at last then, and the load capacity of palladium is 0.9%;
Get the above-mentioned catalyst that makes of 1.5g, 47g phenol, 1g TBAB, 74mg benzoquinones respectively and join in the autoclave of 250ml, feed O
2Pressure be 0.4MPa, the pressure of CO is 5.6MPa, reaction temperature is 120 ℃, reaction pressure is 6MPa, the reaction time is 3 hours.Analysis condition and method are with embodiment 1.The yield of diphenyl carbonate is 15.8%, and catalyst is 99.2% to the selectivity of diphenyl carbonate.
Embodiment 3
Adopt the direct mechanical polishing to prepare the Mn-Pb bimetallic oxide, get 3.2g MnCO
3, other gets 1.8g PbCO
3, with two kinds of salt mixing and stirring on grinder, with mixture in vacuum drying chamber in 100 ℃ of dryings 12 hours; Again with dry thing in Muffle furnace in 400 ℃ of following roastings 8 hours, promptly make manganese system complex oxide catalyst carrier;
Get PdCl
240mg is dissolved in the 40ml deionized water, with concentrated hydrochloric acid its pH value of solution value is dripped to about 1 heating for dissolving again, the above-mentioned manganese system complex oxide catalyst carrier that makes is added in the solution, adding NaOH aqueous slkali adjusting pH value then is 9, precipitate active component, and ceaselessly stirred 3 hours, then filtration, drying, obtained final catalyst in 3 hours 200 ℃ of following roastings at last, the load capacity of palladium is 0.5%;
Get the above-mentioned catalyst that makes of 1.0g, 47g phenol, 1g TBAB, 74mg benzoquinones respectively and join in the autoclave of 250ml, feed O
2Pressure be 0.3MPa, the pressure of CO is 4.7MPa, reaction temperature is 100 ℃, reaction pressure is 5MPa, the reaction time is 4 hours.Analysis condition and method are with embodiment 1, and the yield of diphenyl carbonate is 14.7%, and catalyst is 98.5% to the selectivity of diphenyl carbonate.
Embodiment 4
Adopt the direct mechanical polishing to prepare the Mn-Pb bimetallic oxide, get 3.2g MnCO
3, other gets 1.8g PbCO
3, with two kinds of salt mixing and stirring on grinder, with mixture in vacuum drying chamber in 100 ℃ of dryings 10 hours; Again with dry thing in Muffle furnace in 400 ℃ of following roastings 8 hours, promptly make manganese system complex oxide catalyst carrier;
Get PdCl
240mg is dissolved in the 40ml deionized water, with concentrated hydrochloric acid its pH value of solution value is dripped to about 1 heating for dissolving again, the above-mentioned manganese system complex oxide catalyst carrier that makes is added in the solution, flooded 12 hours, filter then, drying, obtained final catalyst in 3 hours 200 ℃ of following roastings at last, the load capacity of palladium is 0.7%;
Get the above-mentioned catalyst that makes of 1.0g, 47g phenol, 1g TBAB, 74mg benzoquinones respectively and join in the autoclave of 250ml, feed O
2Pressure be 0.2MPa, the pressure of CO is 3.8MPa, reaction temperature is 90 ℃, reaction pressure is 4MPa, the reaction time is 3.5 hours.Analysis condition and method are with embodiment 1, and the yield of diphenyl carbonate is 15.7%, and catalyst is 98.5% to the selectivity of diphenyl carbonate.
Embodiment 5
Adopt the direct mechanical polishing to prepare the Mn-Pb bimetallic oxide, get 3.2g MnCO
3, other gets 1.8g PbCO
3, with two kinds of salt mixing and stirring on grinder, with mixture in vacuum drying chamber in 100 ℃ of dryings 12 hours; Again with dry thing in Muffle furnace in 400 ℃ of following roastings 8 hours, promptly make manganese system complex oxide catalyst carrier;
Get PdCl
240mg and the above-mentioned mixing of manganese system complex oxide catalyst carrier, the drying of making obtained final catalyst in 3 hours 200 ℃ of following roastings at last, and the load capacity of palladium is 0.8%;
Get the above-mentioned catalyst that makes of 1.5g, 47g phenol, 1g TBAB, 74mg benzoquinones respectively and join in the autoclave of 250ml, feed O
2Pressure be 0.3MPa, the pressure of CO is 5.7MPa, reaction temperature is 70 ℃, reaction pressure is 6MPa, the reaction time is 5 hours.Analysis condition and method are with embodiment 1, and the yield of diphenyl carbonate is 16.4%, and catalyst is 97.4% to the selectivity of diphenyl carbonate.
Embodiment 6
Adopt the direct mechanical polishing to prepare the Mn-Cu-Pb composite metal oxide, get 2.5g MnCO
3, other gets 1.0g Cu
2(OH)
2CO
3With 1.5g PbCO
3With three kinds of salt mixing and stirring on grinder, with mixture in vacuum drying chamber in 100 ℃ of dryings 12 hours; Again with dry thing in Muffle furnace in 600 ℃ of following roastings 5 hours, promptly make manganese system and close the oxide catalyst carrier;
Get PdCl
240mg is dissolved in the 40ml deionized water, with concentrated hydrochloric acid its pH value of solution value is dripped to about 1 heating for dissolving again, the above-mentioned manganese system complex oxide catalyst carrier that makes is added in the solution, adding NaOH aqueous slkali adjusting pH value then is 8, precipitate active component, and ceaselessly stirred 4 hours, then filtration, drying, obtained final catalyst in 5 hours 300 ℃ of following roastings at last, the load capacity of palladium is 0.7%;
Get the above-mentioned catalyst that makes of 2.0g, 47g phenol, 1g TBAB, 74mg benzoquinones respectively and join in the autoclave of 250ml, feed O
2Pressure be 0.2MPa, the pressure of CO is 3.8MPa, reaction temperature is 80 ℃, reaction pressure is 4MPa, the reaction time is 4 hours.Analysis condition and method are with embodiment 1, and the yield of diphenyl carbonate is 16.9%, and catalyst is 98.7% to the selectivity of diphenyl carbonate.
Embodiment 7
Adopt the direct mechanical polishing to prepare the Mn-Co bimetallic oxide, get 4.2g MnCO
3, other gets 0.8g CoCO
3, with two kinds of salt mixing and stirring on grinder, with mixture in vacuum drying chamber in 100 ℃ of dryings 12 hours; Again with dry thing in Muffle furnace in 600 ℃ of following roastings 7 hours, promptly make the bimetal composite oxide catalyst carrier;
Get PdCl
240mg is dissolved in the 40ml deionized water, with concentrated hydrochloric acid its pH value of solution value is dripped to about 1 heating for dissolving again, above-mentioned carrier is added wherein, add the NaOH aqueous slkali then with the precipitation active component, regulating the pH value is 9, and ceaselessly stirs 5 hours, filters then, filter cake drying in drying box is obtained final catalyst, and the load capacity of palladium is 1%;
Get the above-mentioned catalyst that makes of 1.4g, 47g phenol, 1g TBAB, 74mg benzoquinones respectively and join in the autoclave of 250ml, feed O
2Pressure be 0.4MPa, the pressure of CO is 5.6MPa, reaction temperature is 120 ℃, reaction pressure is 6MPa, the reaction time is 3 hours.Analysis condition and method are with embodiment 1, and the yield of diphenyl carbonate is 7.4%, and catalyst is 94.57% to the selectivity of diphenyl carbonate.
Embodiment 8
Adopt the direct mechanical polishing to prepare the Mn-Cr bimetallic oxide, get 3.4g MnCO
3, other gets 1.6g Cr (NO
3)
39H
2O, with two kinds of salt mixing and stirring on grinder, with mixture in vacuum drying chamber in 100 ℃ of dryings 10 hours; Again with dry thing in Muffle furnace in 600 ℃ of following roastings 7 hours, promptly make the bimetal composite oxide catalyst carrier;
Get NaPdCl
440mg is dissolved in the 40ml deionized water, with concentrated hydrochloric acid its pH value of solution value is dripped to about 1, heating for dissolving again, the above-mentioned bimetal composite oxide catalyst carrier that makes is added in the solution, and adding NaOH aqueous slkali adjusting pH value then is 9, precipitates active component, and ceaselessly stirred 5 hours, filter then, filter cake drying in drying box is obtained final catalyst, the load capacity of palladium is 0.5%;
Get the above-mentioned catalyst that makes of 1.6g, 47g phenol, 1g TBAB, 74mg benzoquinones respectively and join in the autoclave of 250ml, feed O
2Pressure be 0.3MPa, the pressure of CO is 4.7MPa, reaction temperature is 100 ℃, reaction pressure is 5MPa, the reaction time is 4 hours.Analysis condition and method are with embodiment 1, and the yield of diphenyl carbonate is 13.5%, and catalyst is 96.2% to the selectivity of diphenyl carbonate.
Embodiment 9
Adopt the direct mechanical polishing to prepare the Mn-Ni bimetallic oxide, get 4g MnCl
24H
2O, other gets 1g Ni (OAc)
26H
2O, with two kinds of salt mixing and stirring on grinder, with mixture in vacuum drying chamber in 100 ℃ of dryings 12 hours; Again with dry thing in Muffle furnace in 400 ℃ of following roastings 8 hours, promptly make manganese system complex oxide catalyst carrier;
Get 40mg Pd (AcO)
2With the above-mentioned mixing of manganese system complex oxide catalyst carrier, the drying of making, obtained final catalyst in 3 hours 200 ℃ of following roastings at last, the load capacity of palladium is 1%;
Get the above-mentioned catalyst that makes of 1.5g, 47g phenol, 1g TBAB, 74mg benzoquinones respectively and join in the autoclave of 250ml, feed O
2Pressure be 0.4MPa, the pressure of CO is 5.6MPa, reaction temperature is 70 ℃, reaction pressure is 6MPa, the reaction time is 5 hours.Analysis condition and method are with embodiment 1, and the yield of diphenyl carbonate is 11.4%, and catalyst is 97.98% to the selectivity of diphenyl carbonate.
Embodiment 10
Adopt indirect mechanical milling method to prepare the Mn-Zn bimetallic oxide, get 4.2g MnCl
24H
2O for how many sodium carbonate liquors precipitates, wears out 10 hours in right amount, filters with concentration, gets the manganese carbonate presoma; Then with manganese carbonate presoma in vacuum drying chamber dry 12 hours; Again with dry thing in Muffle furnace in 600 ℃ of following roastings 7 hours, Mn oxide; Other gets 0.8g ZnCl
2, with two kinds of compounds mixing and stirring on grinder, with mixture in vacuum drying chamber in 100 ℃ of dryings 12 hours; Again with dry thing in Muffle furnace in 500 ℃ of following roastings 8 hours, promptly make manganese system complex oxide catalyst carrier;
Get Pd (AcO)
240mg is dissolved in the 40ml deionized water, with concentrated hydrochloric acid its pH value of solution value is transferred to about 1, heating for dissolving again, above-mentioned manganese system complex oxide catalyst carrier is added in the solution, and adding NaOH aqueous slkali adjusting pH value then is 8, precipitates active component, and ceaselessly stirred 4 hours, filtration, drying obtained final catalyst in 4 hours 300 ℃ of following roastings at last then, and the load capacity of palladium is 0.7%;
Get the above-mentioned catalyst that makes of 1.5g, 47g phenol, 1g TBAB, 74mg benzoquinones respectively and join in the autoclave of 250ml, feed O
2Pressure be 0.4MPa, the pressure of CO is 5.6MPa, reaction temperature is 120 ℃, reaction pressure is 6MPa, the reaction time is 3 hours.Analysis condition and method are with embodiment 1, and the yield of diphenyl carbonate is 9.74%, and catalyst is 97.54% to the selectivity of diphenyl carbonate.
Embodiment 11
Adopt indirect mechanical milling method to prepare the Mn-Bi bimetallic oxide, get 4.2g MnSO
4H
2O, with 4ml concentration be 20% sodium carbonate precipitate, aging 16 hours, filter, the manganese carbonate presoma; Then with manganese carbonate presoma in vacuum drying chamber dry 12 hours; Again with dry thing in Muffle furnace in 600 ℃ of following roastings 7 hours, Mn oxide; Other gets 0.8g Bi
2(SO
4)
3, with two kinds of compounds mixing and stirring on grinder, with mixture in vacuum drying chamber in 100 ℃ of dryings 12 hours; Again with dry thing in Muffle furnace in 500 ℃ of following roastings 8 hours, promptly make manganese system complex oxide catalyst carrier;
Get 40mg K
2PdCl
4With the above-mentioned mixing of manganese system complex oxide catalyst carrier, the drying of making, obtained final catalyst in 3 hours 200 ℃ of following roastings at last, the load capacity of palladium is 1%;
Get the above-mentioned catalyst that makes of 1.5g, 47g phenol, 1g TBAB, 74mg benzoquinones respectively and join in the autoclave of 250ml, feed O
2Pressure be 0.4MPa, the pressure of CO is 5.6MPa, reaction temperature is 70 ℃, reaction pressure is 6MPa, the reaction time is 5 hours.Analysis condition and method are with embodiment 1, and the yield of diphenyl carbonate is 10.1%, and catalyst is 97.5% to the selectivity of diphenyl carbonate.
Claims (9)
1. the catalyst of a heterogeneous oxidative carbonylation diphenyl carbonate synthesis, the manganese that periodic table of elements group VIII Pd salt is carried on as carrier is composite metal oxide, wherein carrier manganese be composite metal oxide by among manganese and oxygen compound and La, Ce, Ti, Zr, V, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Zn, Bi, Pb, the Sn any more than a kind or a kind metal oxide formed, the load capacity of active component Pd is 0.01%-10.0% (wt).
2. require 1 described catalyst according to power, it is characterized in that: the load capacity of active component Pd is: 0.10%-1.0%.
3. require the described Preparation of catalysts method of one of 1-2 according to power, carry out according to the following steps: (1), manganese are the preparation of composite metal oxide carrier: by MnO, MnCl
2, Mn (OAc)
2, MnCO
3, MnSO
4Or Mn (NO
3)
2Solution and La (NO
3)
3, CeO
2, Ce (OAc)
3, Ce (NO
3)
3, TiCl
4, ZrO
2, ZrCl
4, ZrOCl
2, ZrOCO
3, ZrOSO
4, Zr (AC)
4, V
2O
5, VOCl
2, NaVO
3, NaVO
3, NH
4VO
3, VOSO
4, Cr (NO
3)
3, MoO
3, (NH
4)
2MoO
4, Na
2MoO
4, Na
2WO
4, FeCl
3, Fe
2(SO
4)
3, Fe (NO
3)
3, CoO, CoCl
2, Co (OAc)
2, CoSO
4, NiO, Ni (OAc)
2, NiSO
4, Cu
2O, CuO, CuF, CuCl, CuBr, CuI, CuSO
4, CuBr
2, CuCl
2, Cu (OAc)
2, Cu
2(OH)
2CO
3, AgNO
3, ZnCl
2, ZnSO
4, BiO, Bi
2O
3, BiCl
2, BiCl
3, BiSO
4, Bi
2(SO
4)
3, PbO, Pb
3O
4, PbCl
2, Pb (OAc)
2, PbCO
3, Pb
2(OH)
2CO
3, PbSO
4, SnO
2, SnCl
2, SnCl
4In any more than a kind or a kind the solution of compound mix MnO, MnCl
2, Mn (OAc)
2, MnCO
3, MnSO
4Or Mn (NO
3)
2Solution is any ratio with the mol ratio of each selected salting liquid, and with alkali solution precipitate, aging 10-24 hour, filters then, with the gained sediment in vacuum drying chamber in 90～120 ℃ of dryings 2～24 hours; Again with dry thing in Muffle furnace in 200～1000 ℃ of following roastings 2～12 hours, promptly getting manganese is the composite metal oxide carrier; Or, choose MnCO
3Or Mn (NO
3)
2With any oxide, nitrate or carbonate mixing and stirring on grinder of metal more than a kind or a kind among La, Ce, Ti, Zr, V, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Zn, Bi, Pb, the Sn, MnCO
3Or Mn (NO
3)
2With the mol ratio of each selected metallic compound be any ratio, with mixture in vacuum drying chamber in 90～120 ℃ of dryings 2～24 hours; Again with dry thing in Muffle furnace in 200～1000 ℃ of following roastings 2～12 hours, promptly getting manganese is the composite metal oxide carrier; Or, with MnCl
2, Mn (OAc)
2, MnCO
3, MnSO
4Or Mn (NO
3)
2Solution with alkali precipitation, aging 10-24 hour, filter, the manganese and oxygen compound presoma, then with manganese and oxygen compound presoma, manganese carbonate or manganese nitrate in vacuum drying chamber dry 2～24 hours; Again with dry thing in Muffle furnace in 200～1000 ℃ of following roastings 2～12 hours, manganese and oxygen compound; Again with any oxide, nitrate or carbonate mixing and stirring on grinder of metal more than a kind or a kind among manganese and oxygen compound and La, Ce, Ti, Zr, V, Cr, Mo, W, Fe, Co, Ni, Cu, Ag, Zn, Bi, Pb, the Sn; Manganese and oxygen compound is any ratio with the mol ratio of the metallic compound of respectively selecting for use, with mixture in vacuum drying chamber in 90～120 ℃ of dryings 2～24 hours; Again with dry thing in Muffle furnace in 200～1000 ℃ of following roastings 2～12 hours, promptly getting manganese is the composite metal oxide carrier; (2) active substance palladium salt being loaded to the manganese that is made by (1) step is on the O composite metallic oxide catalyst carrier, and drying at 200～600 ℃ of following roasting 1-8 hours, promptly gets required solid catalyst again.
4. method according to claim 3 is characterized in that: described active substance palladium salt is PdCl
2, Pd (AcO)
2, NaPdCl
4, K
2PdCl
4, (NH
4)
4PdCl
4, (NH
4)
2PdCl
6, (Nbu
4)
2PdCl
4In any one.
5. method according to claim 3, it is characterized in that: described active substance palladium salt is loaded to manganese is on the O composite metallic oxide catalyst carrier, be that to be loaded to manganese by infusion process, the precipitation method or multifuel combustion method be on the O composite metallic oxide catalyst carrier, infusion process is: with the manganese that makes is that composite metal oxide carrier concentration is 0.001mol/L-1mol/L active material PdCl
2, Pd (AcO)
2Or NaPdCl
4Solution impregnation, filtration, drying got final product at 200-500 ℃ of following roasting 2-6 hour at last then; The precipitation method: with the manganese that makes is that composite metal oxide carrier concentration is 0.001mol/L-1mol/L active material PdCl
2, Pd (AcO)
2Or NaPdCl
4Solution impregnation drips an amount of precipitating reagent while stirring, and the pH that keeps solution is deposited on the carrier active component at 8-9, filters then, washs, drying, gets final product at 200-500 ℃ of following roasting 2-6 hour at last, and used precipitating reagent is NaOH, KOH, NH
3H
2O, NH
4HCO
3In any one; The multifuel combustion method; With active material PdCl
2, Pd (AcO)
2Or NaPdCl
4With manganese is that the composite metal oxide carrier is 0.02-16.5 by weight: 100 mix, and get final product at 200-500 ℃ of following roasting 2-6 hour.
6. method according to claim 3 is characterized in that: described alkali is any one in ammonium carbonate, carbonic hydroammonium, ammoniacal liquor, alkali-metal hydroxide, alkali-metal carbonate, alkali-metal bicarbonate and the urea.
7. method according to claim 3 is characterized in that: after the carrying active substance palladium salt, the sintering temperature of catalyst is 200～500 ℃, and roasting time is 2-6 hour.
8. method according to claim 3 is characterized in that: manganese is that drying time, sintering temperature and roasting time are respectively 8-12 hour, 300～700 ℃ and 4-8 hour in the composite metal oxide preparing carriers process.
9. heterogeneous oxidative carbonylation diphenyl carbonate synthesis method is characterized in that: used the described catalyst of claim 1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100537806A CN101147870A (en) | 2007-11-07 | 2007-11-07 | Catalyst for synthesizing diphenyl carbonate used in non-homogeneuos oxidation carbonylation and method for preparing the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100537806A CN101147870A (en) | 2007-11-07 | 2007-11-07 | Catalyst for synthesizing diphenyl carbonate used in non-homogeneuos oxidation carbonylation and method for preparing the same |
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| Publication Number | Publication Date |
|---|---|
| CN101147870A true CN101147870A (en) | 2008-03-26 |
Family
ID=39248637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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| Country | Link |
|---|---|
| CN (1) | CN101147870A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102441380A (en) * | 2011-11-07 | 2012-05-09 | 武汉工程大学 | Forming method for synthesizing diphenyl carbonate heterogeneous catalyst by catalytic oxidation |
| CN103071497A (en) * | 2012-12-31 | 2013-05-01 | 天津大学 | Activated carbon load single valence state cuprous oxide chloride-free catalyst, preparation method, and application in oxidate oxo synthesis dimethyl carbonate |
| CN103611532A (en) * | 2013-11-15 | 2014-03-05 | 河北工业大学 | Catalyst for synthesizing diphenyl carbonate in phenol oxidative carbonylation as well as preparation method and application method of catalyst |
| CN110252320A (en) * | 2019-07-02 | 2019-09-20 | 滕州京腾鑫汇新材料科技有限公司 | A kind of catalyst of Synthesis of dimethyl carbonate and preparation method thereof |
| CN110339858A (en) * | 2019-07-17 | 2019-10-18 | 河南科技学院 | Bi for synthesis of methyl phenyl carbonic ester2O3- PbO-SBA-15 catalyst, preparation method and application |
-
2007
- 2007-11-07 CN CNA2007100537806A patent/CN101147870A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102441380A (en) * | 2011-11-07 | 2012-05-09 | 武汉工程大学 | Forming method for synthesizing diphenyl carbonate heterogeneous catalyst by catalytic oxidation |
| CN102441380B (en) * | 2011-11-07 | 2013-04-10 | 武汉工程大学 | Forming method for synthesizing diphenyl carbonate heterogeneous catalyst by catalytic oxidation |
| CN103071497A (en) * | 2012-12-31 | 2013-05-01 | 天津大学 | Activated carbon load single valence state cuprous oxide chloride-free catalyst, preparation method, and application in oxidate oxo synthesis dimethyl carbonate |
| CN103611532A (en) * | 2013-11-15 | 2014-03-05 | 河北工业大学 | Catalyst for synthesizing diphenyl carbonate in phenol oxidative carbonylation as well as preparation method and application method of catalyst |
| CN103611532B (en) * | 2013-11-15 | 2015-05-27 | 河北工业大学 | Catalyst for synthesizing diphenyl carbonate in phenol oxidative carbonylation as well as preparation method and application method of catalyst |
| CN110252320A (en) * | 2019-07-02 | 2019-09-20 | 滕州京腾鑫汇新材料科技有限公司 | A kind of catalyst of Synthesis of dimethyl carbonate and preparation method thereof |
| CN110339858A (en) * | 2019-07-17 | 2019-10-18 | 河南科技学院 | Bi for synthesis of methyl phenyl carbonic ester2O3- PbO-SBA-15 catalyst, preparation method and application |
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