CN1775734A - Method for synthesizing diphenyl carbonate from phenol oxidation carbonylation by environment friendly solvent process - Google Patents
Method for synthesizing diphenyl carbonate from phenol oxidation carbonylation by environment friendly solvent process Download PDFInfo
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- CN1775734A CN1775734A CNA2005101221820A CN200510122182A CN1775734A CN 1775734 A CN1775734 A CN 1775734A CN A2005101221820 A CNA2005101221820 A CN A2005101221820A CN 200510122182 A CN200510122182 A CN 200510122182A CN 1775734 A CN1775734 A CN 1775734A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides a method for synthesizing diphenyl carbonate by phenol carbon oxide oxidative carbonylation in environmental friendly solvent, selecting conventional organic solvent or supercritical CO2 fluid as the environmental friendly solvent, making phenol, metallic auxiliary catalyst, organic auxiliary catalyst, surface active agent, and CO react with O2 at high pressure to produce the diphenyl carbonate. The invention mainly solves the problems of environmental pollution, and Pd loss. The produced diphenyl carbonate has higher yield and the environmental friendly solvent has the advantages of low toxicity, no pollution, being easy to be separated from the products, being able to circularly utilize, etc.
Description
Technical field
The invention belongs to a kind of development and application of environmentally friendly solvent, particularly a kind of method of synthesizing diphenyl carbonate from phenol oxidation carbonylation by environment friendly solvent process.
Background technology
Diphenyl carbonate is a kind of important environmental protective chemical industry product, can be used for synthetic many important medicine, agricultural chemicals and other organic compound and macromolecular material.The synthetic method of diphenyl carbonate has phosgenation, ester-interchange method and phenol oxidation carbonylation method.There are shortcomings such as complex process, raw material phosgene severe toxicity, serious environment pollution in phosgenation, is eliminated just gradually; Ester-interchange method uses methylcarbonate or dimethyl oxalate to be raw material, the cost height, and speed of reaction is low, and catalyzer and reaction unit are had special requirement; The phenol oxidation carbonylation method has that technology is simple, raw material cheaply reaches free of contamination characteristics, but has equilibrium conversion low, catalyzer and product difficult separation and recycling and shortcoming such as contaminate environment with an organic solvent when adopting homogeneous catalyst at present.If can address the above problem, the phenol oxidation carbonylation method will become one of diphenyl carbonate synthetic method that has development prospect most.
The Primary Catalysts of phenol oxidation carbonylation method diphenyl carbonate synthesis catalyst system is the metal and the compound thereof of VIII family, wherein is mainly the compound of Pd and Pd.Because catalyzer costliness, diphenyl carbonate productive rate hang down and the catalyzer efficiency of conversion is not high, make the technology of phenol oxidation carbonylation method diphenyl carbonate synthesis not see the industrialization report as yet.U.S. Pat 5132447 proposes Pd (OAc)
2/ Co (OAc)
2/ TBAB homogeneous catalyst system is used for the catalysis of phenol oxidation carbonylation, finds that the adding of benzoquinones can make the DPC productive rate bring up to 19.0% by 15.2%, but catalyst deactivation is speeded up.U.S. Pat 5284964 finds that the diphenyl carbonate productive rate obviously improves, and especially adopts Pd (OAc) in the presence of three pyridines
2/ CoSMDPT (2-salicylic aldehyde)-3,3 '-two amidos-when N-methyl (dipropylamine) cobalt/TBAB/ (Tetrabutyl amonium bromide) three pyridine systems were made catalyzer, the diphenyl carbonate productive rate can reach 45%.Iwane etc. (Iwane H, Miyagi H, Imada S, Seo S, Yoneyama T.EP 0614876.1993) adopt porous carrier, as gac, Al
2O
3, SiO
2Even load metal Pd catalysis of phenol oxidation carbonylation, the DPC productive rate is 12.6% to the maximum.(Takagi M such as Takagi, Miyagi H, Yoneyama T, Ohgomori Y.Journal Molecular Catalysis A:Chemical, 1998,129:L1-L3) adopting 5%Pd/C is Primary Catalysts, and PbO is a pro-oxidant, obtained 9.55% DPC productive rate, and pointed out that Pd/C is identical with homogeneous phase Pd catalyst action mechanism.Song etc. (Song H Y, Park E D, Lee J S.Journal Molecular Catalysis A:Chemical, 2000,154:243-250) surface characteristic and the distribution of Pd on carrier of discovery carrier are most important to catalytic activity.On hydrophobic absorbent charcoal carrier, catalyst activity is apparently higher than hydrophilic γ-Al
2O
3And SiO
2In carrier.(Ishii H, Ueda M, Takeuchi K, Asai M.Catalysis Communications, 2001 (2), 17-22 such as Ishii; Ishii H, Takeuchi K, M Asai, Ueda M.Catalysis Communications, 2001 (2), 145-150) adopting high molecular polymer is carrier, the title complex that will contain Pd is grafted on carrier surface, be used for the DPC building-up reactions, find when there is pyridinium chloride in polystyrene surface, also can not carry out smoothly even do not add the ammonium halide salt reaction.Zhang Guangxu etc. (Zhang Guangxu, Wu Yuanxin, Ma Peisheng, Wu Guangwen. catalysis journal, 2002,23 (2): 130-132; The chemistry of fuel journal, 2002,30 (4): 363-367; Journal of Molecular Catalysis, 2002,16 (4): 293-297; The catalysis journal, 2002,23 (5): 413-416) prepared the LaxMnyPbzO composite oxide carrier with sol-gel method, by the precipitator method with the Pd load thereon, be used for the DPC building-up reactions, DPC productive rate and selectivity are respectively 7.2% and 93%.
Utilize the phenol oxidation carbonylation legal system to be equipped with diphenyl carbonate in the above-mentioned document, great majority are to adopt methylene dichloride as solvent.(20 ℃, 47Pa), gaseous exhaust is its main mode that enters environment for the boiling point of methylene dichloride low (40.1 ℃), vapour pressure height.Methylene dichloride belongs to the lower toxicity material, but the narcoticness of its steam is strong, and a large amount of suctions can cause acute poisoning, symptoms such as nasal cavity pain, headache, vomiting occur; Can cause during chronic poisoning that dim eyesight, tired, poor appetite, hemopoietic function are impaired, red blood corpuscle minimizing etc.Current, methylene dichloride is considered to the bigger halogenated hydrocarbon material of topsoil toxic.In addition,, can dissolve the metal oxide active ingredient in the heterogeneous catalyst, cause loss of active component, shorten catalyst life because the polarity of methylene dichloride is stronger.
In sum, phenol oxidation carbonylation method reaction diphenyl carbonate synthesis uses dichloromethane solvent, has problems such as unfriendly to environment, that the noble metal active component runs off easily, catalyst life is short at present.
Summary of the invention
The objective of the invention is to solve problems such as the reaction solvent that exists in the existing phenol oxidation carbonylation reaction diphenyl carbonate synthesis technology is unfriendly to environment, the noble metal active component runs off easily, catalyst life is short, thereby provide a kind of in environment amenable solvent, utilize the method for phenol oxidation carbonylation reaction diphenyl carbonate synthesis.
Technical solution of the present invention is as follows: the method for synthesizing diphenyl carbonate from phenol oxidation carbonylation by environment friendly solvent process is characterized by and adopts in the following steps any one:
Reactions steps when (1) selecting conventional organic solvent as environmentally friendly solvent comprises:
Wherein add component and consumption is as follows:
The amounts of components proportioning
Phenol 100～2000
Catalyzer 1
Metal promoters 1～20
Organic promoter 1～60
Tensio-active agent 1～60
(i) take by weighing phenol, catalyzer, metal promoters, organic promoter and tensio-active agent according to the above ratio and place autoclave, ratio in 0.5～10 gram dewatering agent/gram phenol and 1～50 milliliter of solvent/gram phenol takes by weighing dewatering agent and environmentally friendly solvent again, and adds in the autoclave;
(ii) in autoclave, charge into O
2And CO, O
2With the pressure ratio of CO be 1: 10～30, the dividing potential drop of CO is 2～6MPa, sealing post-heating to 60～160 ℃ keep temperature, the reaction times is 2～20 hours, obtains reaction product;
Perhaps
(2) use supercritical CO
2Fluid is as environmentally friendly solvent, and its reactions steps comprises as follows:
Wherein add component and consumption is as follows:
The amounts of components proportioning
Phenol 100～2000
Catalyzer 1
Metal promoters 1～20
Organic promoter 1～60
Tensio-active agent 1～60
(i) take by weighing phenol, catalyzer, metal promoters, organic promoter and tensio-active agent according to the above ratio and place autoclave, the ratio in 0.5～10 gram dewatering agent/gram phenol takes by weighing dewatering agent again, and adds in the autoclave;
(ii) in autoclave, charge into O
2And CO, O
2With the pressure ratio of CO be 1: 10～30, the dividing potential drop of CO is 2～6MPa, sealing post-heating to 60～160 ℃ keep temperature;
(iii) open CO
2Cylinder valve makes CO
2After the low temperature thermostat bath cooling liquid, enter pressurised metered pump, start volume pump to CO
2Be forced into 30.0Mpa, open the volume pump outlet valve again and the autoclave intake valve charges into CO
2, the still internal pressure is closed all valves after reaching 8～25.0Mpa, timing begin the reaction, react 2～20 hours, be cooled to room temperature with frozen water after, still is driven in pressure release, the taking-up reaction mixture.
The conventional organic solvent as environmentally friendly solvent described in the step of the present invention (1) is methylcarbonate, diethyl carbonate, Methyl ethyl carbonate or propylene carbonate.
The method of phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent of the present invention is when environmentally friendly solvent is a supercritical CO
2During fluid, in step (i), also comprise in reaction system, adding cosolvent, be used for increasing phenol, catalyzer, metal promoters, organic promoter and tensio-active agent at supercritical CO
2Solubleness in the fluid, add-on are 0.5～5 milliliter of cosolvent/gram phenol.
The method of phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent of the present invention is when environmentally friendly solvent is a supercritical CO
2During fluid, described cosolvent is ethanol, methyl alcohol, acetonitrile, methylcarbonate, diethyl carbonate or Methyl ethyl carbonate.
The method of phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent of the present invention, described catalyzer is Palladous chloride, palladium bromide, palladium iodide, acid chloride, Palladous nitrate or heterogeneous catalyst Pd-Cu-O/SiO
2
The method of phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent of the present invention, described metal promoters is venus crystals, cupric nitrate, copper sulfate, cupric chloride, manganous acetate, cobaltous acetate, zinc acetate, lead acetate or cerous acetate.
The method of phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent of the present invention, described organic promoter is Resorcinol, benzoquinones, anthraquinone, naphthoquinones, pyridine, terpyridyl, quinoline or isoquinoline 99.9.
The method of phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent of the present invention, described tensio-active agent is Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide or tetrabutyl acetyl ammonium.
The method of phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent of the present invention, described dewatering agent is 4A molecular sieve, 3A molecular sieve or 5A molecular sieve.
The method of phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent of the present invention, with the methylcarbonate is solvent, Palladous chloride is a catalyzer, venus crystals is a metal promoters, Resorcinol is an organic promoter, Tetrabutyl amonium bromide is a tensio-active agent, and the 4A molecular sieve is a dewatering agent.
The present invention compared with prior art has following beneficial effect:
1. reaction solvent environmental sound, cost is low, and reaction effect is good, good reproducibility.The used solvent of the present invention all belongs to green chemical, especially supercritical CO
2, both can directly discharge, also can reclaim, recycle, environmentally friendly.In environmentally friendly solvent, phenol oxidation carbonylation reaction diphenyl carbonate synthesis has higher activity, and repeatability is good.
2. the noble metal active component runs off less in the heterogeneous catalyst.The present invention is with in the reaction solvent, and noble metal active component Pd can reduce loss in the heterogeneous catalyst in reaction process, keeps its activity, prolongs life.Catalyzer can be reused more than 3 times, only needs with behind the solvent wash, and dry, roasting can recover active.
Embodiment
PdCl in embodiment 1 dimethyl carbonate solvent
2The catalysis of phenol oxidation carbonylation
1. take by weighing 0.005 gram PdCl
2, placing volume is 100 milliliters tank reactor, adds 2.4 gram phenol, 20 milliliters of methylcarbonates, 0.2384 gram Tetrabutyl amonium bromides (TBAB), 0.5546 gram Resorcinol (H again in reactor
2BQ) and 4 gram 4A molecular sieves;
2. in reactor, charge into O
2Pressure is 0.3Mpa, and CO pressure is 3.6Mpa, and sealing post-heating to 80 ℃ keeps temperature, reacts 4 hours;
3. after reaction finished, with SP3420 type gas chromatographic analysis reaction solution, external standard method was quantitative, and the productive rate of diphenyl carbonate is 32.2%.
Embodiment 2-5
The chemical reagent consumption is identical with embodiment 1 with reactions steps, but changes catalyzer (make the consumption of Pd identical with embodiment 1), and its reactivity worth sees Table 1.
Table 1 different catalysts is to the influence of the synthetic DPC productive rate of phenol oxidation carbonylation in the dimethyl carbonate solvent
| Catalyzer | Palladous chloride | Palladous nitrate | Palladium bromide | Palladium iodide | Acid chloride |
| Consumption/g | 0.005 | 0.0075 | 0.0075 | 0.010 | 0.006 |
| DPC *Productive rate/% | 32.2 | 23.3 | 18.6 | 14.4 | 15.6 |
| Embodiment | 1 | 2 | 3 | 4 | 5 |
*DPC: diphenyl carbonate
Embodiment 6-9
The chemical reagent consumption is identical with embodiment 1 with reactions steps, but changes temperature of reaction, and the remaining reaction condition is identical with embodiment 1, and its reactivity worth sees Table 2.
Table 2 differential responses temperature is to the influence of the synthetic DPC productive rate of phenol oxidation carbonylation in the dimethyl carbonate solvent
| Temperature of reaction/℃ | 60 | 70 | 80 | 90 | 100 |
| DPC productive rate/% | 17.7 | 28.3 | 32.2 | 30.2 | 26.3 |
| Embodiment | 6 | 7 | 1 | 8 | 9 |
Embodiment 10-13
The chemical reagent consumption is identical with embodiment 1 with reactions steps, but changes CO and O
2Initial partial pressure (CO and O
2Mol ratio constant), the remaining reaction condition is identical with embodiment 1, its reactivity worth sees Table 3.
Table 3CO dividing potential drop is to the influence of the synthetic DPC productive rate of phenol oxidation carbonylation in the dimethyl carbonate solvent
| CO dividing potential drop/MPa | 1.2 | 2.4 | 3.6 | 4.8 | 6.0 |
| DPC productive rate/% | 15.2 | 21.3 | 32.2 | 35.2 | 38.3 |
| Embodiment | 10 | 11 | 1 | 12 | 13 |
Embodiment 14-17
The chemical reagent consumption is identical with embodiment 1 with reactions steps, but changes the consumption of methylcarbonate, and the remaining reaction condition is identical with embodiment 1, and its reactivity worth sees Table 4.
The influence of the synthetic DPC productive rate of table 4 methylcarbonate consumption Pyrogentisinic Acid oxidative carbonylation
| Methylcarbonate consumption/ml | 10 | 20 | 30 | 40 | 50 |
| DPC productive rate/% | 5.7 | 32.2 | 27.8 | 25.1 | 20.4 |
| Embodiment | 14 | 1 | 15 | 16 | 17 |
Heterogeneous catalyst Pd-Cu-O/SiO in embodiment 18 dimethyl carbonate solvent
2The catalysis of phenol oxidation carbonylation
1. heterogeneous catalyst Pd-Cu-O/SiO
2Preparation see document (Xue Wei, Wang Yanji etc. the chemical industry journal, 2004,55 (12): 2076), the quality percentage composition of Pd is 0.6%;
2. take by weighing 0.5 gram Pd-Cu-O/SiO
2, make the Pd consumption identical with embodiment 1, it is 100 milliliters tank reactor that catalyzer is placed volume, adds 2.4 gram phenol again in reactor, 20 milliliters of methylcarbonates, 0.2384 gram Tetrabutyl amonium bromides (TBAB) and 0.5546 restrain Resorcinol (H
2BQ);
3. in reactor, charge into O
2Pressure is 0.3Mpa, and CO pressure is 3.6Mpa, and sealing post-heating to 80 ℃ keeps temperature, reacts 4 hours;
4. after reaction finished, with SP3420 type gas chromatographic analysis reaction solution, external standard method was quantitative, and the productive rate of diphenyl carbonate is 25.3%.
Heterogeneous catalyst Pd-Cu-O/SiO in embodiment 19 dimethyl carbonate solvent
2Repeat performance
Select the catalyzer among the embodiment 18 for use, reaction times is 4 hours, other reaction conditions is identical with embodiment 18, but carry out the multiple reaction experiment 3 times, after promptly each reaction finishes with catalyzer with the methylcarbonate thorough washing after, to constant weight, place 500 ℃ of following roastings of retort furnace to regenerate in 5 hours 60 ℃ of vacuum-dryings again.Catalyzer after the regeneration is used for secondary response down, and the result shows that the productive rate of diphenyl carbonate slightly descends when catalyzer is reused, but the amplitude that reduces is very little, the results are shown in Table 5.
Pd-Cu-O/SiO in table 5 dimethyl carbonate solvent
2The repeated use effect of catalyzer
| The catalyzer access times | 1 | 2 | 3 | 4 |
| DPC productive rate/% | 25.3 | 23.5 | 21.6 | 22.0 |
Embodiment 20 supercritical COs
2PdCl in the solvent
2The catalysis of phenol oxidation carbonylation
1. take by weighing 0.005 gram PdCl
2, placing volume is 100 milliliters tank reactor, adds 2.4 gram phenol, 0.2384 gram Tetrabutyl amonium bromide (TBAB), 0.5546 gram Resorcinol (H again in reactor
2BQ) and 4 gram 4A molecular sieves;
2. in reactor, charge into O
2Pressure is 0.3Mpa, and CO pressure is 3.6Mpa, and sealing post-heating to 80 ℃ keeps temperature.Open CO
2Cylinder valve makes CO
2After the low temperature thermostat bath cooling liquid, enter pressurised metered pump.Start volume pump to CO
2Be forced into 30.0MPa, open the volume pump outlet valve and the reactor intake valve charges into CO
2, close all valves after making the reaction system stagnation pressure reach 16MPa, timing begins reaction;
3. behind the reaction certain hour, be cooled to room temperature with frozen water after, still is driven in pressure release, takes out reaction mixture.With SP3420 type gas chromatographic analysis reaction solution, external standard method is quantitative, and the productive rate of diphenyl carbonate is 15.7%.
Embodiment 21-25
The chemical reagent consumption is identical with embodiment 20 with reactions steps, charges into CO but change
2Afterreaction system stagnation pressure, its reactivity worth sees Table 6.
Table 6 reaction system stagnation pressure is to supercritical CO
2The influence of middle synthesizing diphenyl carbonate from phenol oxidation carbonylation productive rate
| Stagnation pressure/MPa | 8 | 10 | 12 | 14 | 16 | 18 |
| DPC productive rate/% | 5.6 | 5.2 | 8.9 | 8.6 | 15.7 | 15.3 |
| Embodiment | 21 | 22 | 23 | 24 | 20 | 25 |
Embodiment 26 cosolvent are to supercritical CO
2PdCl in the solvent
2The influence of catalysis of phenol oxidation carbonylation
Add the 5mL methylcarbonate as cosolvent in reaction system, all the other chemical reagent consumptions are identical with embodiment 20 with reactions steps, and the productive rate of diphenyl carbonate is 19.8%.
Embodiment 27 supercritical COs
2Pd-Cu-O/SiO in the solvent
2The catalysis of phenol oxidation carbonylation
1. heterogeneous catalyst Pd-Cu-O/SiO
2Preparation see document (Xue Wei, Wang Yanji etc. the chemical industry journal, 2004,55 (12): 2076), the quality percentage composition of Pd is 0.6%; Take by weighing 0.5 the gram this catalyzer, make the Pd consumption with
Embodiment 20 is identical, and remaining reaction condition, operation steps are identical with embodiment 20;
2. with SP3420 type gas chromatographic analysis reaction solution, external standard method is quantitative, and the productive rate of diphenyl carbonate is 8.7%.
Embodiment 28
Select the catalyzer among the embodiment 27 for use, take by weighing 0.5 gram, make the Pd consumption identical with embodiment 20, remaining reaction condition, operation steps are identical with embodiment 20, but carry out the multiple reaction experiment 3 times, after finishing, promptly each reaction, to constant weight, place 500 ℃ of following roastings of retort furnace to regenerate in 5 hours again 60 ℃ of vacuum-dryings with behind the catalyzer usefulness methylcarbonate thorough washing.Catalyzer after the regeneration is used for secondary response down, and the result shows that activity of such catalysts of the present invention and selectivity remain unchanged substantially, the results are shown in Table 7 when reusing.
Table 7 supercritical CO
2Middle Pd-Cu-O/SiO
2The repeated use effect of catalyzer
| The catalyzer access times | 1 | 2 | 3 | 4 |
| DPC productive rate/% | 8.7 | 8.5 | 8.2 | 7.8 |
Claims (10)
1, a kind of method of synthesizing diphenyl carbonate from phenol oxidation carbonylation by environment friendly solvent process is characterized by and adopts in the following steps any one:
Reactions steps when (1) selecting conventional organic solvent as environmentally friendly solvent comprises:
Wherein add component and consumption is as follows:
The amounts of components proportioning
Phenol 100～2000
Catalyzer 1
Metal promoters 1～20
Organic promoter 1～60
Tensio-active agent 1～60
(i) take by weighing phenol, catalyzer, metal promoters, organic promoter and tensio-active agent according to the above ratio and place autoclave, ratio in 0.5～10 gram dewatering agent/gram phenol and 1～50 milliliter of solvent/gram phenol takes by weighing dewatering agent and environmentally friendly solvent again, and adds in the autoclave;
(ii) in autoclave, charge into O
2And CO, O
2With the pressure ratio of CO be 1: 10～30, the dividing potential drop of CO is 2～6MPa, sealing post-heating to 60～160 ℃ keep temperature, the reaction times is 2～20 hours, obtains reaction product;
(2) adopt supercritical CO
2The reactions steps of fluid during as environmentally friendly solvent comprises:
Wherein add component and consumption is as follows:
The amounts of components proportioning
Phenol 100～2000
Catalyzer 1
Metal promoters 1～20
Organic promoter 1～60
Tensio-active agent 1～60
(i) take by weighing phenol, catalyzer, metal promoters, organic promoter and tensio-active agent according to the above ratio and place autoclave, the ratio in 0.5～10 gram dewatering agent/gram phenol takes by weighing dewatering agent again, and adds in the autoclave;
(ii) in autoclave, charge into O
2And CO, O
2With the pressure ratio of CO be 1: 10～30, the dividing potential drop of CO is 2～6MPa, sealing post-heating to 60～160 ℃ keep temperature;
(iii) open CO
2Cylinder valve makes CO
2After the low temperature thermostat bath cooling liquid, enter pressurised metered pump, start volume pump to CO
2Be forced into 30.0Mpa, open the volume pump outlet valve again and the autoclave intake valve charges into CO
2, the still internal pressure is closed all valves after reaching 8～25.0Mpa, timing begin the reaction, react 2～20 hours, be cooled to room temperature with frozen water after, still is driven in pressure release, the taking-up reaction mixture.
2, the method for phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent according to claim 1, it is characterized in that: the conventional organic solvent as environmentally friendly solvent described in the step (1) is methylcarbonate, diethyl carbonate, Methyl ethyl carbonate or propylene carbonate.
3, the method for phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent according to claim 1 is characterized in that: when environmentally friendly solvent is a supercritical CO
2During fluid, in step (i), comprise also in reaction system, adding cosolvent that add-on is 0.5～5 milliliter of cosolvent/gram phenol.
4, the method for phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent according to claim 3, it is characterized in that: described cosolvent is ethanol, methyl alcohol, acetonitrile, methylcarbonate, diethyl carbonate, Methyl ethyl carbonate.
5, the method for phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent according to claim 1, it is characterized in that: described catalyzer is Palladous chloride, palladium bromide, palladium iodide, acid chloride, Palladous nitrate or heterogeneous catalyst Pd-Cu-O/SiO
2
6, the method for phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent according to claim 1, it is characterized in that: described metal promoters is venus crystals, cupric nitrate, copper sulfate, cupric chloride, manganous acetate, cobaltous acetate, zinc acetate, lead acetate or cerous acetate.
7, the method for phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent according to claim 1, it is characterized in that: described organic promoter is Resorcinol, benzoquinones, anthraquinone, naphthoquinones, pyridine, terpyridyl, quinoline or isoquinoline 99.9.
8, the method for phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent according to claim 1, it is characterized in that: described tensio-active agent is Tetrabutyl amonium bromide, tetrabutylammonium chloride, tetrabutylammonium iodide or tetrabutyl acetyl ammonium.
9, the method for phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent according to claim 1, it is characterized in that: described dewatering agent is 4A molecular sieve, 3A molecular sieve or 5A molecular sieve.
10, the method for phenol oxidation carbonylation reaction diphenyl carbonate synthesis in the environmentally friendly solvent according to claim 1, it is characterized in that: be solvent with the methylcarbonate, Palladous chloride is a catalyzer, venus crystals is a metal promoters, Resorcinol is an organic promoter, Tetrabutyl amonium bromide is a tensio-active agent, and the 4A molecular sieve is a dewatering agent.
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| CN102140065A (en) * | 2010-01-29 | 2011-08-03 | 中国石油化学工业开发股份有限公司 | Preparation method of diaryl carbonate |
| CN102557949A (en) * | 2010-12-28 | 2012-07-11 | 中国石油化学工业开发股份有限公司 | Process for producing diaryl carbonate |
| CN102580775A (en) * | 2011-12-30 | 2012-07-18 | 河北工业大学 | Schiff base complex catalyst for synthesizing diphenyl carbonate through oxidative carbonylation of phenol |
| CN103012127A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for subjecting phenol and dimethyl ester to transesterification |
| CN104364194A (en) * | 2012-05-02 | 2015-02-18 | 赫多特普索化工设备公司 | Process for the production of chemical compounds from carbon dioxide |
| CN114931975A (en) * | 2022-04-13 | 2022-08-23 | 河南科技学院 | Catalyst for synthesizing diphenyl carbonate, preparation method and application of diphenyl carbonate |
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2005
- 2005-12-06 CN CNA2005101221820A patent/CN1775734A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140065A (en) * | 2010-01-29 | 2011-08-03 | 中国石油化学工业开发股份有限公司 | Preparation method of diaryl carbonate |
| CN102140065B (en) * | 2010-01-29 | 2013-07-24 | 中国石油化学工业开发股份有限公司 | Preparation method of diaryl carbonate |
| CN102557949A (en) * | 2010-12-28 | 2012-07-11 | 中国石油化学工业开发股份有限公司 | Process for producing diaryl carbonate |
| CN102557949B (en) * | 2010-12-28 | 2014-12-31 | 中国石油化学工业开发股份有限公司 | Process for producing diaryl carbonate |
| CN103012127A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for subjecting phenol and dimethyl ester to transesterification |
| CN103012127B (en) * | 2011-09-28 | 2015-08-26 | 中国石油化工股份有限公司 | A kind of phenol and dimethyl ester carry out the method for transesterify |
| CN102580775A (en) * | 2011-12-30 | 2012-07-18 | 河北工业大学 | Schiff base complex catalyst for synthesizing diphenyl carbonate through oxidative carbonylation of phenol |
| CN104364194A (en) * | 2012-05-02 | 2015-02-18 | 赫多特普索化工设备公司 | Process for the production of chemical compounds from carbon dioxide |
| US9273020B2 (en) | 2012-05-02 | 2016-03-01 | Haldor Topsoe A/S | Process for the production of chemical compounds from carbon dioxide |
| CN104364194B (en) * | 2012-05-02 | 2016-09-14 | 赫多特普索化工设备公司 | The method being prepared compound by carbon dioxide |
| CN114931975A (en) * | 2022-04-13 | 2022-08-23 | 河南科技学院 | Catalyst for synthesizing diphenyl carbonate, preparation method and application of diphenyl carbonate |
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