CN1255210C - Preparing method for loaded titania catalyst of ester interchange synthetic phenyl ester oxalate - Google Patents
Preparing method for loaded titania catalyst of ester interchange synthetic phenyl ester oxalate Download PDFInfo
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- CN1255210C CN1255210C CN 200410019331 CN200410019331A CN1255210C CN 1255210 C CN1255210 C CN 1255210C CN 200410019331 CN200410019331 CN 200410019331 CN 200410019331 A CN200410019331 A CN 200410019331A CN 1255210 C CN1255210 C CN 1255210C
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 150000002148 esters Chemical class 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 25
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title 1
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 5
- LJCNULUFLCOAKC-UHFFFAOYSA-N 1-o-methyl 2-o-phenyl oxalate Chemical compound COC(=O)C(=O)OC1=CC=CC=C1 LJCNULUFLCOAKC-UHFFFAOYSA-N 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000000741 silica gel Substances 0.000 claims description 6
- 229910002027 silica gel Inorganic materials 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 238000002803 maceration Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 206010013786 Dry skin Diseases 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001887 tin oxide Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 30
- YVWNBNDYTKPZFP-UHFFFAOYSA-N 2-oxo-2-phenoxyacetic acid Chemical compound OC(=O)C(=O)OC1=CC=CC=C1 YVWNBNDYTKPZFP-UHFFFAOYSA-N 0.000 abstract description 11
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 abstract description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 9
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000010936 titanium Substances 0.000 abstract description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000969 carrier Substances 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 238000001354 calcination Methods 0.000 abstract 1
- 230000003197 catalytic effect Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 230000007062 hydrolysis Effects 0.000 abstract 1
- 238000006460 hydrolysis reaction Methods 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 125000003944 tolyl group Chemical group 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical class COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 229960001866 silicon dioxide Drugs 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- BPCNGVCAHAIZEE-UHFFFAOYSA-N [(5-methyl-2-propan-2-ylcyclohexyl)-phenylphosphoryl]benzene Chemical compound CC(C)C1CCC(C)CC1P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 BPCNGVCAHAIZEE-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 organic acid compound Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention discloses a preparation method of coated titanium dioxide catalysts for synthesizing oxalic acid phenyl ester through ester exchange, and belongs to a technique for preparing methyl phenyl oxalic ester and phenyloxalate catalysts for synthesizing diphenyl carbonate (DPC). The preparation method is a hydrolysis method, and mainly comprises the following steps of preparing titanium precursor steeping liquor, pretreating carriers and mixing, hydrolyzing, drying and calcining the steeping liquor and the carriers. The coated titanium dioxide catalysts prepared by the present invention have high catalytic activity for phenol and dimethyl oxalate to synthesize oxalic acid phenyl ester through ester exchange, so the yield of the oxalic acid phenyl ester is higher than 50%. The present invention has the advantages of bland operating conditions, no pollution to environment, no corrosion to equipment, low cost, easy separation of the catalysts from reaction systems, catalyst recovery and reutilization, etc.
Description
Technical field
The present invention relates to a kind of ester exchange synthesis of oxalic acid phenyl ester load type titania Catalysts and its preparation method, specifically, relate to synthetic raw material methyl phenyl oxalate (MPO) and the phenostal (DPO) of producing diphenyl carbonate (DPC) of dimethyl oxalate under the heterogeneous conditions (DMO) and phenol ester exchange and use the Preparation of catalysts method.
Background technology
With dimethyl oxalate and phenol is that feedstock production methyl phenyl oxalate and phenostal are that all are the key technology of feedstock production diphenyl carbonate with dimethyl oxalate and phenol.The reactions steps of this key technology experience is as follows:
With this key technology is that the dpc production technology of core occurred in the nineties, but development rapidly, particularly Ri Ben Ube company is devoted to the research of this respect always, and applied for many patents, as EP1013633A1, US5811573, CN1164529A, TW438765, US5834615, EP0832872A1, US5922827, EP0832910A2 etc.But in above-mentioned all patents, relating to the dimethyl oxalate is raw material prepares diphenyl carbonate synthesis by ester exchange raw material, when being methyl phenyl oxalate or phenostal, though used ester exchange catalyst is brought in constant renewal in, variation is also perfect, can be alkali metal, cadmium, zirconium, plumbous, iron, copper, zinc compound or organo-tin compound, aluminium, titanium, the organic acid compound of vanadium etc., but be the homogeneous catalyst that dissolves in reaction system, promptly the ester exchange reaction that will carry out to some extent be homogeneous reaction, thereby above-mentioned all patented technologies have all used complicated piece-rate system or equipment that catalyst is separated with reaction.The inventor mentions in 02129212.4 patent and adopts titanium deoxide catalyst catalysis synthesis of oxalic acid phenyl ester, has that selectivity is good, the yield advantages of higher, but does not mention this Preparation of catalysts method.
Summary of the invention
The object of the present invention is to provide a kind of ester exchange synthesis of oxalic acid phenyl ester load type titania Preparation of catalysts method.This method operating condition gentleness, the catalyst activity height that technical process is simple, prepared, selectivity is good.
Prepare the method for catalysis synthesis of oxalic acid phenyl ester with the load type titania catalyst, this catalyst carrier is selected from a kind of in magnesia, active carbon, Alpha-alumina or gama-alumina, silica gel, tin oxide, molecular sieve, the zirconia, and its active component content of titanium dioxide is at 1-20wt%.It is to form with the Hydrolyze method preparation, it is characterized in that comprising process:
(1) be that the carrier granular of 30～100 is placed in the drying box in 60～200 ℃ of dryings 2～8 hours with particle diameter, standby;
(2) take by weighing butyl titanate and be dissolved in the absolute ethyl alcohol, be mixed with the mixed solution that molar concentration is 0.03～0.6mol/L, be maceration extract after fully stirring;
(3) press carrier and butyl titanate mol ratio: 1: (0.008～0.2) adds dry good carrier and mixes with maceration extract, after at room temperature stirring 1～2 hour in the nitrogen stream, press butyl titanate and deionized water mol ratio: 1: (1～8) under agitation drips deionized water;
(4) mixed liquor after will fully stirring left standstill 24～72 hours in the nitrogen stream under room temperature, obtained pressed powder;
(5) with this pressed powder in 60～200 ℃ dry 4～12 hours down, send into again in the Muffle furnace in 300～800 ℃ of following roastings 5 hours; Promptly make the support type titanium oxide catalyst.
Above-mentioned carrier is a silica gel.
Above-mentioned carrier and butyl titanate mol ratio are 1: (0.06～0.14).
Above-mentioned butyl titanate and deionized water be in molar ratio: 1: (4～8).
Above-mentioned sintering temperature is 500～600 ℃.
The invention has the advantages that, adopt Hydrolyze method to prepare the load type titania catalyst, have operating condition gentleness, environmentally safe, equipment had the burn into technical process is simple, low cost and other advantages.Raw material phenyl oxalate by employing load type titania catalytic synthesis of C diphenyl phthalate is methyl phenyl oxalate and phenostal, not only conversion of raw material and product selectivity all have and adopt homogeneous catalyst significantly to improve, and separating technology process and equipment have been save to the complexity of catalyst and reaction system, reduced production cost, the industrialization of Pyrogentisinic Acid and phenostal ester exchange has far reaching significance.
Come the present invention is further specified below by specific embodiment, but do not limit the present invention.
The specific embodiment
Preparation of [embodiment 1] support type titanium oxide catalyst and active the investigation
The present invention prepares phenol and dimethyl oxalate ester exchange synthesis of oxalic acid phenyl ester is investigated with the enforcement of support type titanium oxide catalyst.The silica-gel carrier particle is as for 120 ℃ of dryings in the drying box, standby.Take by weighing 0.86 gram butyl titanate and be dissolved in the 80ml absolute ethyl alcohol, at room temperature stir 0.5h in the nitrogen stream, the particle diameter of putting into 20g is the good silica-gel carriers of 80 preliminary treatment, fully stir 2h after, slowly drip the ethanolic solution that contains the 0.4g deionized water.Mixed liquor after fully stirring was left standstill 24～72 hours in the nitrogen stream under room temperature, obtain pressed powder, with this solid in 60～200 ℃ dry 5 hours down, send into again in the Muffle furnace in 550 ℃ of following roastings 5 hours, promptly making the titanium dichloride load amount is the support type titanium oxide catalyst of 1wt%.
The present invention is to be that the enforcement of feedstock production methyl phenyl oxalate and phenostal process is investigated with dimethyl oxalate and phenol under the heterogeneous catalytic reaction condition, in 250 milliliters there-necked flask, carry out, the heating of heat collecting type electromagnetic agitation, chuck is furnished with thermometer, to show the reaction system temperature.The consumption of technical grade DMO is 0.1 mole, and the amount of chemical pure phenol is 0.3 mole, metal oxide supporting catalyst TiO
2/ SiO
2Consumption be 1.8 the gram, under normal pressure, add, wherein the load capacity of titanium dioxide is 1%.Stir and heat up, reaction temperature is controlled at 180.0 ± 2 ℃, and the reaction time is 2 hours.For improving conversion of raw material, mouth is equipped with the reflux condensing tube of the thermostatical circulating water that feeds 80 ℃ (a little more than boiling points of by-product methyl alcohol) in the flask, and the gas that reaction generates partly distillates by reflux condensation mode, and collects distillate in cold-trap.The cold-trap outlet connects triple valve, and gas phase analysis is got at the place at triple valve.After reaction finished, by filtration under diminished pressure separating reaction material and catalyst, filtrate was the mixture of product and unreacting material.Determine reactant liquor, the gentle phase composition of liquid distillate by gas chromatography instrument and gas-chromatography.With the conversion ratio of DMO, the selectivity of MPO, DPO is index, investigates reactivity worth.
[embodiment 2-8]
Change metal oxide supporting catalyst TiO
2/ SiO
2The load capacity of middle titanium oxide is respectively 4%, 8%, 10%, 12%, 14%, 16%, 18%, and under other condition and the embodiment 1 identical situation, carries out ester exchange reaction, forms embodiment 2-8 respectively, investigates reaction result.
Table 1:TiO
2/ SiO
2Catalyst series catalyzed transesterification result (weight percentage)
| Embodiment | Titania oxide supported amount, % | DMO conversion ratio % | Selectivity, % | Yield, % | |||
| Methyl phenyl ethers anisole | MPO | DPO | MPO | DPO | |||
| 1 2 3 4 5 6 7 8 | 1 4 8 10 12 14 16 18 | 45.9 46.5 52.5 62.3 66.3 63.9 60.3 53.8 | 0.6 0.8 0.9 0.9 0.4 0.4 0.6 0.4 | 79.0 77.4 75.7 73.6 71.9 73.1 76.7 76.2 | 19.7 21.5 23.0 23.9 27.3 26.2 22.4 22.9 | 36.3 36.0 39.7 45.9 47.7 46.7 46.3 41.0 | 9.0 10.0 12.1 14.9 18.1 16.7 13.5 12.3 |
[embodiment 9-13]
It is 16% TiO that catalyst is used titania oxide supported amount instead
2/ MgO loaded catalyst, TiO
2/ Al
2O
3Loaded catalyst, TiO
2/ SnO
2Loaded catalyst, TiO
2/ ZrO
2Loaded catalyst and TiO
2/ C loaded catalyst.Under other condition and embodiment 1 identical situation, carry out ester exchange reaction and form embodiment 9-13 respectively, investigate reaction result.
Table 2: different carriers support type titanium oxide catalyst ester exchange reaction result (weight percentage)
| Embodiment | Catalyst | DMO conversion ratio % | Selectivity, % | Yield, % | |||
| Methyl phenyl ethers anisole | MPO | DPO | MPO | DPO | |||
| 9 10 11 | TiO 2/MgO TiO 2/Al 2O 3 TiO 2/SnO 2 | 62.4 62.2 49.7 | 6.4 19.6 0.3 | 74.3 55.2 69.0 | 18.2 19.4 29.2 | 46.4 34.3 34.3 | 11.4 12.1 14.5 |
| 12 13 | TiO 2/ZrO 2 TiO 2/C | 45.8 56.9 | 1.0 0.9. | 73.4 71.6 | 25.2 23.5 | 33.6 40.7 | 11.5 13.4 |
From the foregoing description reaction result as can be seen, when making catalyst with load metal oxide in the process of the present invention, reaction result preferably can both be arranged.Wherein, for all active metal components, with SiO
2For the catalyst of carrier has embodied higher activity and purpose selectivity of product.
[Comparative Examples 1-5]
Adopt AlCl respectively
3, Zn (OAc)
2, Ti (OC
4H
9)
4, SnOBu
2Make ester exchange catalyst with dibutyl tin laurate, the loadings of catalyst is 0.01mol, under other condition and embodiment 1 identical situation, carries out the homogeneous phase ester exchange reaction.The reaction result of Comparative Examples is as shown in table 5.
Table 5: Comparative Examples ester exchange reaction result
| Comparative Examples | Catalyst | DMO conversion ratio % | Selectivity, % | Yield, % | |||
| Accessory substance | MPO | DPO | MPO | DPO | |||
| 1 2 3 4 5 | AlCl 3 Zn(OAc) 2 Ti(OC 4H 9) 4 SnOBu 2Dibutyl tin laurate | 79.8 28.1 92.5 25.7 54.1 | 67.1 43.5 76.6 6.7 65.3 | 30.8 53.9 20.6 80.8 21.0 | 2.1 2.6 2.8 12.5 13.7 | 24.6 16.4 19.0 20.8 11.4 | 1.7 0.1 2.6 3.2 7.4 |
From embodiment and Comparative Examples as can be seen, be in the technology of feedstock production diphenyl carbonate with dimethyl oxalate and phenol, key technology wherein, be in the step of dimethyl oxalate and phenol ester exchange preparation methyl phenyl oxalate and phenostal, if adopting support type silica is heterogeneous catalysis, the purpose product selectivity exceeds the selectivity in the Comparative Examples far away, and its activity is also higher, thereby higher purpose product yield is arranged.And if with traditional ester exchange catalyst, as be widely used as organic zinc, organic titanium and the organic tin compound as catalyst of ester exchange catalyst, from Comparative Examples 1～5 as can be seen, except that Dibutyltin oxide, the purpose selectivity of product of other catalyst is all extremely low; And Dibutyltin oxide is when making catalyst, and except that costing an arm and a leg, Dibutyltin oxide decomposes voluntarily and forms homogeneous phase with system, outside catalyst can not reclaim, also needs complicated piece-rate system and equipment.
To sum up, load type titania with the Hydrolyze method preparation is the ester exchange reaction of passing through phenol and dimethyl oxalate of feature as ester exchange catalyst, synthetic methyl phenyl oxalate and the phenostal that is used to prepare diphenyl carbonate, for by being raw material with dimethyl oxalate and phenol, elder generation's synthesis of methyl phenyl oxalate and phenostal, by further preparing diphenyl carbonate, provide more favourable key core technology then with phenol ester exchange and/or direct de-carbonyl reaction.
The invention is not restricted to above embodiment, present patent application personnel can make various changes and distortion according to the present invention, only otherwise break away from spirit of the present invention, all should belong to scope of the present invention.
Claims (5)
1. ester exchange synthesis of methyl phenyl oxalate and phenostal are with load type titania Preparation of catalysts method, this catalyst carrier is selected from a kind of in magnesia, active carbon, Alpha-alumina or gama-alumina, silica gel, tin oxide, molecular sieve, the zirconia, its active component content of titanium dioxide is at 1-20wt%, it is to form with the Hydrolyze method preparation, and its feature comprises following process:
(1) be that the carrier granular of 30～100 is placed in the drying box in 60～200 ℃ of dryings 2～8 hours with particle diameter, standby;
(2) take by weighing butyl titanate and be dissolved in the absolute ethyl alcohol, be mixed with the mixed solution that molar concentration is 0.03～0.6mol/L, be maceration extract after fully stirring;
(3) be that the dry good carrier of 1: 0.008～0.2 adding mixes with maceration extract by carrier and butyl titanate mol ratio, after at room temperature stirring 1～2 hour in the nitrogen stream, by butyl titanate and deionized water mol ratio is 1: 1～8, under agitation drips deionized water;
(4) mixed liquor after will fully stirring left standstill 24～72 hours in the nitrogen stream under room temperature, obtained pressed powder;
(5) with this pressed powder in 60～200 ℃ dry 4～12 hours down, send into again in the Muffle furnace in 300～800 ℃ of following roastings 5 hours; Promptly make the support type titanium oxide catalyst.
2. according to claim 1 described ester exchange synthesis of methyl phenyl oxalate and phenostal load type titania Preparation of catalysts method, it is characterized in that: carrier is a silica gel.
3. according to claim 1 described ester exchange synthesis of methyl phenyl oxalate and phenostal load type titania Preparation of catalysts method, it is characterized in that: carrier and butyl titanate mol ratio are 1: 0.06～0.14.
4. according to claim 1 described ester exchange synthesis of methyl phenyl oxalate and phenostal load type titania Preparation of catalysts method, it is characterized in that: butyl titanate and deionized water are 1: 4～8 in molar ratio.
5. according to claim 1 described ester exchange synthesis of methyl phenyl oxalate and phenostal load type titania Preparation of catalysts method, it is characterized in that: sintering temperature is 500～600 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410019331 CN1255210C (en) | 2004-05-25 | 2004-05-25 | Preparing method for loaded titania catalyst of ester interchange synthetic phenyl ester oxalate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410019331 CN1255210C (en) | 2004-05-25 | 2004-05-25 | Preparing method for loaded titania catalyst of ester interchange synthetic phenyl ester oxalate |
Publications (2)
| Publication Number | Publication Date |
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| CN1583246A CN1583246A (en) | 2005-02-23 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101564685B (en) * | 2008-08-13 | 2011-04-13 | 中国科学院城市环境研究所 | Method for preparing photocatalytic material of titanium oxide immobilized on fly ash |
| CN101954275A (en) * | 2010-09-28 | 2011-01-26 | 江苏丹化煤制化学品工程技术有限公司 | Method for preparing catalyst used for gas phase catalytic synthesis of diphenyl oxalate from dimethyl oxalate |
| CN104109570B (en) * | 2014-06-26 | 2016-03-30 | 国家电网公司 | The preparation method of nano-titanium oxide modification transformer oil |
| CN104178245B (en) * | 2014-06-26 | 2016-04-13 | 国家电网公司 | The preparation method of nano-titanium oxide concentrated solution modification transformer oil |
| CN106076304B (en) * | 2016-06-16 | 2018-10-09 | 四川理工学院 | Transesterification supported titanium2The preparation method of catalyst |
| CN107321342A (en) * | 2017-07-07 | 2017-11-07 | 四川理工学院 | A kind of support type MoO for synthesis of oxalic acid diphenyl ester3The preparation method of catalyst |
| CN108250075A (en) * | 2018-03-02 | 2018-07-06 | 山东科技大学 | Phenol and dimethyl oxalate exchange synthesis air lift reaction method |
| CN110252274B (en) * | 2019-06-14 | 2022-09-02 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | Preparation method of catalyst for synthesizing diphenyl carbonate by ester exchange |
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