CN101491761A - Bimetal composite oxides catalyst for methyl benzol carbonate disproportionation - Google Patents
Bimetal composite oxides catalyst for methyl benzol carbonate disproportionation Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- NHZZUJIRMHDTKR-UHFFFAOYSA-N carbonic acid;toluene Chemical compound OC(O)=O.CC1=CC=CC=C1 NHZZUJIRMHDTKR-UHFFFAOYSA-N 0.000 title claims description 26
- 238000007323 disproportionation reaction Methods 0.000 title claims description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000010949 copper Substances 0.000 claims abstract description 27
- 229910000464 lead oxide Inorganic materials 0.000 claims abstract description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 7
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 229940046892 lead acetate Drugs 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000906 Bronze Inorganic materials 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- 239000010974 bronze Substances 0.000 claims description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 3
- 229960004643 cupric oxide Drugs 0.000 claims description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 229940112669 cuprous oxide Drugs 0.000 claims description 3
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 claims description 3
- XMFOQHDPRMAJNU-UHFFFAOYSA-N lead(ii,iv) oxide Chemical compound O1[Pb]O[Pb]11O[Pb]O1 XMFOQHDPRMAJNU-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 229910000004 White lead Inorganic materials 0.000 claims description 2
- 229940116318 copper carbonate Drugs 0.000 claims description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 2
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 claims description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 21
- 150000002148 esters Chemical class 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000002156 mixing Methods 0.000 abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052802 copper Inorganic materials 0.000 abstract description 3
- 238000000227 grinding Methods 0.000 abstract description 2
- 125000003944 tolyl group Chemical group 0.000 abstract 2
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 abstract 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000003701 mechanical milling Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- -1 titanate ester Chemical class 0.000 description 2
- 240000000146 Agaricus augustus Species 0.000 description 1
- KKDBZWZRJNRBGA-UHFFFAOYSA-L Cl[Ti]Cl.[CH]1C=CC=C1 Chemical compound Cl[Ti]Cl.[CH]1C=CC=C1 KKDBZWZRJNRBGA-UHFFFAOYSA-L 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 102100033979 Protein strawberry notch homolog 1 Human genes 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012850 discrimination method Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a Pb-Cu composite oxide catalyst for disproportionating reaction of methyl phenyl carbonic ester. The basic components of the catalyst comprise lead oxide and copper oxide, wherein the molar ratio of the lead n(Pb) to the copper n(Cu) is between 100 to 1 and 100 to 100, preferably between 100 to 20 and 100 to 50. The catalyst is prepared by a solution mixing method and a mechanical grinding method. The roasting temperature is between 200 and 800 DEG C, and the roasting time is between 2 and 10 hours. The catalyst has high catalytic activity in the disproportionating reaction of the methyl phenyl carbonic ester, and the highest yield of diphenyl carbonate is more than 80 percent. The catalyst is easy to separate and reclaim, and has no corrosion to equipment.
Description
Technical field
The invention belongs to a kind of bimetal composite oxide catalyst, particularly a kind of Pb-Cu composite oxide catalysts that is used for methyl benzol carbonate disproportionation.
Background technology
Diphenyl carbonate is a kind of important engineering plastics intermediate, and nontoxic, non-corrosiveness, pollution-free is the primary raw material of synthesis of bisphenol A type Merlon.Most widely used general, the most ripe method of industrial diphenyl carbonate synthesis remains phosgenation.Though phosgene has good reactivity worth, this method is unfavorable for safety in production and environmental protection.Non-phosgene route diphenyl carbonate synthesis is the developing direction of technology.The non-phosgene of studying morely at present has ester-interchange method and oxidative carbonylation method etc.Wherein the method for dimethyl carbonate and phenol generation ester exchange production diphenyl carbonate has superiority.This reaction is commonly referred to be to be undertaken by two-step reaction.The first step: dimethyl carbonate and phenol carry out ester exchange reaction and make the intermediate methyl benzol carbonate; Second step: bimolecular methyl benzol carbonate carries out disproportionated reaction and generates diphenyl carbonate and dimethyl carbonate, and perhaps methyl benzol carbonate and phenol further react the generation diphenyl carbonate.
The research of ester-interchange method diphenyl carbonate synthesis catalyst system therefor is more.Yao Jie etc. (Yao Jie, high person of outstanding talent, princes and dukes answer .Lewis acid, base catalysis dimethyl carbonate and phenol ester exchange reaction. petrochemical industry, 2002,31 (2): 99～101) find Pb (Ac)
23H
2O has advantages of high catalytic activity and selectivity.The conversion ratio of phenol is 24.80% under optimum reaction condition, and the selectivity of methyl benzol carbonate is 76.49%, and the selectivity of diphenyl carbonate is 23.51%.(NiuHongying, Yao Jie, Wang Yue, et al.Cp such as Niu
2TiCl
2Used as a Catalyst for the TransesterificationBetween Dimethyl Carbonate and Phenol to Diphenyl Carbonate.J Mol Catal A:Chem, 2005,235:240-243) find that it is a kind of catalyst of function admirable that cyclopentadienyl titanium dichloride reacts this; Compare with the titanate ester catalyst, luxuriant titanium class catalyst is more stable in air, thereby is more suitable in industrialization.N-Bu has been compared in researchs such as Mei Fuming
2SnO, Ti (OC
4H
9)
4, AlCl
3, ZnCl
2The catalytic performance of four kinds of compound for catalysis ester exchange synthesizing diphenyl carbonates.Bu wherein
2The catalytic activity of SnO is the highest.Under normal pressure, n in the time of 160～190 ℃ (phenol): n (diphenyl carbonate): n (n-Bu
2SnO)=4: 1: 0.04, reaction time 14h, the conversion ratio of dimethyl carbonate are 48.5%, the productive rate of diphenyl carbonate is 43.0%, methyl benzol carbonate productive rate 5.5%.The selectivity 88.7% of diphenyl carbonate.People such as MinCao (CaoMin, Meng Yuezhong, Lu Yixin.Synthesis of Diphenyl Carbonate from Dimethyl Carbonateand Ph enol Using O
2-Promoted PbO/MgO Catalysts.Catal Commun, 2005,6:802-807) discovery activates the catalytic performance that 4 hour can further strengthen PbO/MgO with oxygen with the PbO/MgO catalyst of coprecipitation preparation under 460 ℃.180 ℃ were reacted 8 to 10 hours down, and the productive rate of methyl benzol carbonate and diphenyl carbonate is respectively 10% and 26.6%.
Most researchers calculate total recovery and overall selectivity to diphenyl carbonate and methyl benzol carbonate as product, and in fact methyl benzol carbonate needs further reaction just can obtain diphenyl carbonate.The ester exchange overall reaction is totally unfavorable on thermodynamics.Because the equilibrium constant of disproportionated reaction is much larger than the equilibrium constant of ester exchange reaction, in order to avoid equilibrium-limited, improve reaction efficiency, two step ester-interchange methods (or claiming ester exchange-discrimination method) route has appearred, dimethyl carbonate earlier generates the intermediate methyl benzol carbonate with the phenol ester exchange, again the methyl benzol carbonate fractionation disproportionated reaction of coming out to carry out separately.Discover, be applicable to that the catalyst of ester exchange reaction not necessarily also has good catalytic effect for disproportionation.Still there is not at present the catalyst report that is specifically applied to the methyl benzol carbonate disproportionation.
Summary of the invention
The object of the present invention is to provide a kind of bimetal composite oxide catalyst that is used for methyl benzol carbonate disproportionation.
Technology path of the present invention is as follows:
Be used for methyl benzol carbonate disproportionation bimetal composite oxide catalyst basic composition is lead oxides and Cu oxide, wherein the lead bronze mol ratio is n (Pb): n (Cu)=100: 1～100, and proportioning is n (Pb): n (Cu)=100: 20～50 preferably.
(1) kind to be used for the step of bimetal composite oxide catalyst of methyl benzol carbonate disproportionation as follows for solution mixing method preparation:
1. be dissolved in parent lead salt and parent mantoquita in the distilled water respectively;
2. two kinds of solution and stream are added mixing stirring in the beaker;
3. mixed solution is placed 60～90 ℃ of baking ovens complete to water evaporates, in 100～130 ℃ of baking ovens dry 2～7 hours subsequently;
In Muffle furnace in 200～800 ℃ of roastings 2～10 hours, product of roasting is taken out porphyrize, promptly make bimetal composite oxide catalyst.
Said parent lead salt of solution mixing method or lead oxides are plumbi nitras, lead acetate, lead chloride, lead orthoplumbate, one or more in brown lead oxide, alpha-oxidation lead and the beta oxidation lead; Parent mantoquita or Cu oxide are one or more in copper nitrate, Schweinfurt green, copper chloride, stannous chloride, cupric iodide, cupric oxide and the cuprous oxide.
The said sintering temperature of solution mixing method is preferably 400～600 ℃.
(2) kind to be used for the step of bimetal composite oxide catalyst of methyl benzol carbonate disproportionation as follows for mechanical milling method preparation:
1. parent lead salt and parent mantoquita are mixed in mortar, add absolute ethyl alcohol, grind, make it evenly mixed;
2. with said mixture in 90～120 ℃ of baking ovens dry 2～6 hours; And in Muffle furnace in 200～800 ℃ of roasting 4h, with the product of roasting porphyrize, promptly make the Pb-Cu bimetal composite oxide catalyst.
Said parent lead salt of mechanical milling method or lead oxides are plumbi nitras, lead acetate, lead chloride, basic lead carbonate, lead orthoplumbate, one or more in brown lead oxide, alpha-oxidation lead and the beta oxidation lead; Parent mantoquita or Cu oxide are one or more in copper nitrate, Schweinfurt green, basic copper carbonate, copper chloride, stannous chloride, cupric iodide, cupric oxide and the cuprous oxide.
The said sintering temperature of mechanical milling method is preferably 400～600 ℃.
According to solution mixing method or the prepared bimetal composite oxide catalyst of mechanical milling method, its service condition is that catalyst and methyl benzol carbonate mol ratio are 0.01～0.1: 1, reaction temperature is 140～200 ℃, and the reaction time is 1～5 hour, and reaction pressure is 0.1～1.0MPa.
The present invention has following characteristics:
1. catalytic activity height.Pb-Cu composite oxide catalysts of the present invention has good active for the catalysis methyl benzol carbonate disproportionation, and the diphenyl carbonate yield is the highest to surpass 80%.
2. catalyst is easy to separate, reclaim.There is the problem of separating, reclaim difficulty with reaction system in homogeneous catalyst, and the used catalyst of the present invention very easily separates with reaction system.
3. to the equipment non-corrosiveness.The used catalyst of the present invention can etching apparatus.
The specific embodiment:
Illustrate the present invention by following examples, but the present invention is not limited to these embodiment.
Embodiment 1
Get 3.35g plumbi nitras and 1.92g Schweinfurt green and be dissolved in respectively in the 20ml distilled water and be mixed with solution, make n (Pb): n (Cu)=1: 1; Two kinds of solution and stream are added mixing stirring in the beaker; Place 80 ℃ of baking ovens complete mixed solution to water evaporates, in 110 ℃ of baking ovens dry 4 hours subsequently; And in Muffle furnace in 600 ℃ of roastings 4 hours, with the product of roasting porphyrize, promptly make the Pb-Cu bimetal composite oxide catalyst.Be connected with nitrogen conduit, thermometer, and the there-necked flask of rectifying column in add methyl benzol carbonate 20g and prepared catalyst 0.6g, nitrogen protection, reaction pressure is 0.1MPa.Reacted 2 hours down at 180 ℃.Constantly steam the dimethyl carbonate of generation in the reaction by rectifying column.Fraction and reactant liquor are all analyzed with Tianjin, island GC1-4B type gas chromatograph, and it is quantitative to proofread and correct normalization method with area.Activity of such catalysts result is as follows: the diphenyl carbonate productive rate is 59.23%.
Embodiment 2
The Preparation of catalysts method is with embodiment 1, the mol ratio of modulation plumbi nitras and Schweinfurt green, n (Pb): n (Cu)=3: 1; Reaction condition and product analysis method are with embodiment 1.Activity of such catalysts result is as follows: the diphenyl carbonate productive rate is 68.57%.
Embodiment 3
The Preparation of catalysts method is with embodiment 1, the mol ratio of modulation plumbi nitras and Schweinfurt green, n (Pb): n (Cu)=4: 1; Reaction condition and product analysis method are with embodiment 1.Activity of such catalysts result is as follows: the diphenyl carbonate productive rate is 81.05%.
Embodiment 4
The Preparation of catalysts method is with embodiment 1, the mol ratio of modulation plumbi nitras and Schweinfurt green, n (Pb): n (Cu)=16: 1; Reaction condition and product analysis method are with embodiment 1.Activity of such catalysts result is as follows: the diphenyl carbonate productive rate is 54.33%.
Embodiment 5
The Preparation of catalysts method is used copper nitrate instead as the copper source with embodiment 1, n (Pb): n (Cu)=4: 1; Be connected with nitrogen conduit, thermometer, and the there-necked flask of rectifying column in add methyl benzol carbonate 20g and prepared catalyst 0.4g, 170 ℃ of reactions 3 hours down.Constantly steam the dimethyl carbonate of generation in the reaction by rectifying column.Product analysis method is with embodiment 1.Activity of such catalysts result is as follows: the diphenyl carbonate productive rate is 52.25%.
Embodiment 6
The Preparation of catalysts method is used lead acetate instead as plumbous source with embodiment 1, n (Pb): n (Cu)=4: 1; Be connected with nitrogen conduit, thermometer, and the there-necked flask of rectifying column in add methyl benzol carbonate 20g and prepared catalyst 0.8g, 160 ℃ of reactions 2.5 hours down.Constantly steam the dimethyl carbonate of generation in the reaction by rectifying column.Product analysis method is with embodiment 1.Activity of such catalysts result is as follows: the diphenyl carbonate productive rate is 76.84%.
Embodiment 7
The Preparation of catalysts method is with embodiment 3, and changing the sintering temperature of catalyst in Muffle furnace is 500 ℃.Reaction condition and product analysis method are with embodiment 1.Activity of such catalysts result is as follows: the diphenyl carbonate productive rate is 56.22%.
Embodiment 8
The Preparation of catalysts method is with embodiment 3, and changing the sintering temperature of catalyst in Muffle furnace is 700 ℃.Reaction condition and product analysis method are with embodiment 1.Activity of such catalysts result is as follows: the diphenyl carbonate productive rate is 62.33%.
Embodiment 9
Get 13.4g plumbi nitras and 1.92g Schweinfurt green, make n (Pb): n (Cu)=4: 1; Mix, in above-mentioned mixed powder, add absolute ethyl alcohol, mixed grinding 0.5～1 hour.Dry 4h in 110 ℃ of baking ovens subsequently; And in Muffle furnace in 600 ℃ of roasting 4h, with the product of roasting porphyrize, promptly make the Pb-Cu bimetal composite oxide catalyst.Reaction condition and product analysis method are with embodiment 1.Activity of such catalysts result is as follows: the diphenyl carbonate productive rate is 64.52%.
Embodiment 10
The Preparation of catalysts method is used lead acetate respectively instead as plumbous source with embodiment 9, and copper nitrate is as the copper source, makes n (Pb): n (Cu)=8: 1.Be connected with nitrogen conduit, thermometer, and the there-necked flask of rectifying column in add methyl benzol carbonate 20g and prepared catalyst 0.7g, 150 ℃ of reactions 4 hours down.Constantly steam the dimethyl carbonate of generation in the reaction by rectifying column.Product analysis method is with embodiment 1.Activity of such catalysts result is as follows: the diphenyl carbonate productive rate is 67.25%.
Claims (5)
1, a kind of bimetal composite oxide catalyst that is used for methyl benzol carbonate disproportionation, it is characterized in that: it basic composition is lead oxides and Cu oxide, and wherein the lead bronze mol ratio is n (Pb): n (Cu)=100: 1～100.
2. bimetal composite oxide catalyst according to claim 1 is characterized in that: in the catalyst lead bronze preferably proportioning be n (Pb): n (Cu)=100: 20～50.
3. bimetal composite oxide catalyst according to claim 1, it is characterized in that: the parent lead salt or the lead oxides that are used to prepare this catalyst are plumbi nitras, lead acetate, lead chloride, basic lead carbonate, lead orthoplumbate, one or more in brown lead oxide, alpha-oxidation lead and the beta oxidation lead.
4. bimetal composite oxide catalyst according to claim 1 is characterized in that: be used for preparing the parent mantoquita of this catalyst or Cu oxide is copper nitrate, Schweinfurt green, basic copper carbonate, copper chloride, stannous chloride, cupric iodide, cupric oxide and cuprous oxide one or more.
5. bimetal composite oxide catalyst according to claim 1, it is characterized in that: the service condition of catalyst is that catalyst and methyl benzol carbonate mol ratio are 0.01～0.1: 1, reaction temperature is 140～240 ℃, reaction time is 1～5 hour, and reaction pressure is 0.1～1.0MPa.
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| CNA2008100452569A CN101491761A (en) | 2008-01-25 | 2008-01-25 | Bimetal composite oxides catalyst for methyl benzol carbonate disproportionation |
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| CNA2008100452569A CN101491761A (en) | 2008-01-25 | 2008-01-25 | Bimetal composite oxides catalyst for methyl benzol carbonate disproportionation |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675116A (en) * | 2011-03-11 | 2012-09-19 | 上海焦化有限公司 | Method for synthesizing diphenyl carbonate by using dimethyl oxalate |
| CN106140133A (en) * | 2015-04-24 | 2016-11-23 | 中国科学院成都有机化学有限公司 | PbO/ZrO for methyl benzol carbonate disproportionation diphenyl carbonate synthesis2catalyst |
| 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 |
-
2008
- 2008-01-25 CN CNA2008100452569A patent/CN101491761A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675116A (en) * | 2011-03-11 | 2012-09-19 | 上海焦化有限公司 | Method for synthesizing diphenyl carbonate by using dimethyl oxalate |
| CN106140133A (en) * | 2015-04-24 | 2016-11-23 | 中国科学院成都有机化学有限公司 | PbO/ZrO for methyl benzol carbonate disproportionation diphenyl carbonate synthesis2catalyst |
| CN106140133B (en) * | 2015-04-24 | 2019-08-06 | 中国科学院成都有机化学有限公司 | A kind of method of methyl benzol carbonate disproportionation diphenyl carbonate synthesis |
| 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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