CN101905155A - Complex metal oxide catalyst for synthesis of diphenyl carbonate by ester exchange reaction and preparation method thereof - Google Patents
Complex metal oxide catalyst for synthesis of diphenyl carbonate by ester exchange reaction and preparation method thereof Download PDFInfo
- Publication number
- CN101905155A CN101905155A CN2009103030351A CN200910303035A CN101905155A CN 101905155 A CN101905155 A CN 101905155A CN 2009103030351 A CN2009103030351 A CN 2009103030351A CN 200910303035 A CN200910303035 A CN 200910303035A CN 101905155 A CN101905155 A CN 101905155A
- Authority
- CN
- China
- Prior art keywords
- titanium
- oxide catalyst
- molybdenum
- acid
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a complex metal oxide catalyst for synthesis of diphenyl carbonate by ester exchange reaction and a preparation method thereof. The catalyst basically consists of a molybdenum-titanium complex oxide, wherein the weight ratio of the molybdenum to the titanium is 100:10-100; the roasting temperature is between 300 and 600 DEG C; base raw materials for preparing the catalyst are a molybdenum compound and a titanium compound; and the preparation method adopts a coprecipitation method or mechanical grinding method. The catalyst has high catalytic activity and good selectivity for the reaction of synthesizing the diphenyl carbonate by ester exchange, and particularly has the advantages of simple preparation method, easy separation and recycling, no environmental pollution, no corrosion to equipment and the like, so the catalyst can be widely applied to production of the diphenyl carbonate.
Description
Technical field
The invention belongs to a kind of O composite metallic oxide catalyst and preparation method thereof, particularly a kind of synthesizing diphenyl carbonate by using ester exchange molybdenum titanium O composite metallic oxide catalyst and preparation method thereof.
Background technology
Diphenyl carbonate [DPC] is nontoxic, pollution-free, is a kind of important " green " chemical products, can be used for synthetic many important organic compounds and macromolecular material, particularly can replace hypertoxic phosgene and the good Merlon of bisphenol-a reaction production performance.
The synthetic method of diphenyl carbonate mainly contains phosgenation, phenol oxidation carbonylation method and ester-interchange method.Because the phosgene severe toxicity can cause serious environmental to pollute, traditional phosgenation is just progressively eliminated.Though phenol oxidation carbonylation method raw material is simple and easy to, atom utilization is also high, the catalyst costliness of its use, and catalytic efficiency is not high, make the use of this method be restricted, and has not yet to see the industrialization report.With phenol and dimethyl carbonate [DMC] is the ester-interchange method of raw material, it is a kind of process route that reaction generates diphenyl carbonate under catalyst action, wherein the methyl alcohol of Sheng Chenging can be used as the raw material of dimethyl carbonate green synthesis process again, thereby can form the synthesis process of " zero-emission ", thereby, this ester-interchange method is considered to the comparatively promising method of present diphenyl carbonate synthesis, and has formed current research focus.
Be in the trans-esterification processes process of raw material with phenol and dimethyl carbonate, dimethyl carbonate and phenol at first generate methyl benzol carbonate [MPC], and intermediate methyl benzol carbonate [MPC] generates diphenyl carbonate through reactions such as disproportionations again.Studies show that the reaction of formation of intermediate methyl benzol carbonate [MPC] is controlled by thermodynamics, the chemical reaction equilibrium constant Kp of this step only is 3 * 10
-4(453k), need adopt the special extract rectification method for improving diphenyl carbonate [DPC] yield, the exploitation effective catalyst, to improve the production operation cost undoubtedly, and the reactivity of dimethyl carbonate carbonyl is lower than phosgene, and the accessory substance methyl phenyl ethers anisole is more, and the process of producing product investment is big, production cost height is unfavorable for the through engineering approaches of production technology.Therefore, this technology is needed badly to improve and is improved, and explores the green synthesis and production process technical research of diphenyl carbonate and still need carry out in a deep going way.
In the world; Dow chemical company is by introducing acetyl group dexterously; that is: make phenylacetate by acetic anhydride and phenol; carry out synthesis of diphenyl carbonate by ester exchange reaction [DPC] by phenylacetate [PA] and dimethyl carbonate [DMC] again; and declared process patent (US 5349102, and US 5276134).Domestic, pilot study was once done at this point by East China University of Science, in airtight high pressure batch reactor, made catalyst with organotin and organic titanic compound, and reaction temperature is to have synthesized diphenyl carbonate under 190 ℃ of conditions, and catalyst has shown certain catalytic performance.The by-product methyl acetate that this process route produces can be recycled by following approach:
(1) methyl acetate is produced phenylacetate with phenol reactant after being cracked into ketenes;
(2) methyl acetate is produced acetic anhydride through carbonylation, and acetic anhydride is produced phenylacetate with phenol reactant again.
The lock out operation of purpose product and accessory substance is simple in the production, be beneficial to the through engineering approaches of product processes, whole process can realize " 100% atom utilization " fully, it is a Green Chemistry process for cleanly preparing route truly, meet the requirement of " atom economy ", have economic worth, this technology has good development and application prospect.
At present, to being raw material with phenylacetate [PA] and dimethyl carbonate [DMC], the research of the catalyst system by the ester-interchange method diphenyl carbonate synthesis is also few, retrieval pertinent literature report, be that disclosing the employed catalyst of this ester exchange reaction system is organic metatitanic acid methyl esters [Ti (OCH in " Process for the preparation of aromatic carbonates " (US 4182726) patent documentation at existing autograph
3)
4], because metatitanic acid methyl esters [Ti (OCH
3)
4] less stable, in air, be easy to the moisture absorption hydrolysis, unstable properties also has been subjected to certain restriction in commercial Application.In existing open source information, also having one piece of autograph is " research of dimethyl carbonate and phenylacetate diphenyl carbonate synthesis " (Shen Rongchun etc., petrochemical industry, 2002, (31) periodical literature 11:897-900) is reported, with Dibutyltin oxide, tetraethyl titanate, butyl titanate etc. is catalyst, is used for dimethyl carbonate and phenylacetate synthesis of diphenyl carbonate by ester exchange reaction.Because the Dibutyltin oxide catalytic performance is not as the titanate ester catalyst, so industrial utilization is worth little, be not used, and catalyst such as the tetraethyl titanate of its use, butyl titanate are still unstable in air, be easy to the moisture absorption hydrolysis, unstable properties is subjected to certain restriction equally in commercial Application.Analyzing existing documents and materials can find, being used for phenylacetate [PA] and dimethyl carbonate [DMC] is raw material, caltalyst by the ester-interchange method diphenyl carbonate synthesis is a homogeneous catalyst system, because the homogeneous catalyst that relates in use will be dissolved in reaction system, reaction finishes, catalyst and product separate, reclaim comparatively difficulty.So the commercial application prospect of homogeneous catalyst is not too optimistic.Make a general survey of chemical reaction synthetic catalyst system, heterogeneous catalyst is easy to separate and reclaims, the development trend that meets the green chemical industry cleaner production more, in industrial production, have broad application prospects, it is one of the focus and emphasis in current catalyticing research field, and be used for phenylacetate [PA] and dimethyl carbonate [DMC] is raw material, and the research report of the relevant heterogeneous catalyst of the reaction system by the ester-interchange method diphenyl carbonate synthesis is still blank.Therefore, to being raw material with phenylacetate [PA] and dimethyl carbonate [DMC], catalyst system by the ester-interchange method diphenyl carbonate synthesis, particularly the research and development of heterogeneous catalyst system need deeply launch, and it is very necessary to explore the metastable new and effective heterogeneous catalyst system with prospects for commercial application of exploitation.
Summary of the invention
Reclaim difficulty for solving the catalyst separation that exists in the prior art, cost an arm and a leg, problem such as unstable properties, the invention provides a kind of ester exchange reaction heterogeneous catalysis complex metal oxide catalyst for synthesis of diphenyl carbonate and preparation method.
Realize that the technical scheme that the object of the invention is taked is:
Compound metal oxide catalyst for synthesizing diphenyl carbonate by using ester exchange basic composition is molybdenum oxide and titanium oxide, and wherein the weight ratio of molybdenum and titanium is: Mo: Ti=100: 10-100.
The step for preparing O composite metallic oxide catalyst with the precipitation method is as follows:
(1) the parent molybdenum compound is dissolved in the distilled water, is made into the solution of 10%-50% (mass percent);
(2) be made into the acid solution of 10%-40% (percent by volume) with a kind of in distilled water and acetic acid, hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, the citric acid or their mixture;
(3) above-mentioned two kinds of solution are mixed with cocurrent process, add organic titanic compound Ti (OR) simultaneously
4, stir precipitation, vacuum filtration;
(4) with the gained sediment in baking oven 90-120 ℃ dry 12 hours down;
(5) with dried sediment or gel in Muffle furnace in 300-600 ℃ of roasting temperature 3-8 hour, take out and promptly make O composite metallic oxide catalyst.
Parent molybdenum compound described in the precipitation method is molybdic acid, ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate, sodium molybdate, potassium molybdate etc.
Organic titanic compound Ti (OR) described in the precipitation method
4In R be carbon number smaller or equal to 4 alkyl substituent.
The step that mechanical milling method prepares O composite metallic oxide catalyst is as follows:
(1) parent molybdenum salt is dissolved in the distilled water, is made into the solution of 10%-40% (mass percent);
(2) use distilled water and acetic acid, nitric acid, hydrochloric acid, sulfuric acid to prepare the acid solution of 10%-40% (percent by volume);
(3) above-mentioned two kinds of solution are pressed cocurrent process and mixed stirring, form molybdate compound precipitation or gel, vacuum filtration;
(4) with organic titanic compound Ti (OR)
4, a kind of in the halogenated titanium, titanium sulfate, Titanium Nitrate, titanium phosphate, phosphoric acid-oxygen-titanium, titanyl sulfate or their mixture add in the distilled water, heats up and stir, and forms titanium-containing compound precipitation or gel, vacuum filtration;
(5) will (3), filter back gained sediment in (4), wash respectively, drying;
(6) two kinds of change things that make in (5) are ground in mortar, mix;
(7) mixture after will grinding again in Muffle furnace in 300-600 ℃ of roasting temperature 3-8 hour, take out and promptly get molybdenum-titanium O composite metallic oxide catalyst.
Parent molybdenum compound described in the mechanical milling method is molybdic acid, ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate, sodium molybdate, potassium molybdate etc.
Organic titanic compound Ti (OR) described in the mechanical milling method
4Middle R is alkyl, alkoxy substituent.
Compare with existing public technology, the present invention has following advantage:
1, catalyst is active high.Molybdenum-titanium compound oxide catalyst used in the present invention is to being raw material with phenylacetate [PA] and dimethyl carbonate [DMC], have good catalytic performance by ester exchange reaction heterogeneous catalytic method diphenyl carbonate synthesis, can reach more than 95% the overall selectivity of carbonic acid phenyl ester.
2, catalyst is easy to separate, reclaim, and is reusable, good stability.The used heterogeneous catalyst of the present invention has overcome exist in the homogeneous catalyst use difficult to problems such as product purity impact because of separating, reclaiming, all exist before and after the reaction with solid form, reaction finishes and very easily separates with product, only need simple heat treatment just can recover activity of such catalysts, can reuse repeatedly.
3, catalyst is environmentally friendly, not etching apparatus.The used multiphase oxide catalyst of the present invention can etching apparatus and contaminated environment except that low toxicity own.
Therefore, the present invention has good economic benefit and social benefit.
The specific embodiment
Enumerate the specific embodiment that a plurality of embodiment further specify the inventive method below, and the superperformance effect of embodiment catalyst.It is to be noted that the inventive method is not limited to cited embodiment.
Embodiment 1:
1, takes by weighing 20.0 gram ammonium molybdate ((NH
4)
6Mo
7O
24H
2O) (contain about 11 grams of molybdenum) and be dissolved in the distilled water, be made into the solution of 30% (mass percent); Then its 20% (percent by volume) acetum with preparation is mixed with cocurrent process, Dropwise 5 0ml tetrabutyl titanate (about 7.0 grams of titaniferous) stirs precipitation, vacuum filtration simultaneously; With gained sediment or gel in baking oven in 90-120 ℃ of drying 12 hours; With dried sediment in Muffle furnace in 400 ℃ of roasting temperatures 3 hours, take out and promptly get molybdenum-titanium O composite metallic oxide catalyst.
2, take by weighing the autoclave that 110.0 gram phenylacetates (about 0.80mol), 12.0 gram dimethyl carbonates (about 0.13mol) and 5.0 restraints molybdenum-titanium compound oxide catalyst fully join the subsidiary intelligent constant-temperature controller of 250ml, seal with securing member, after with nitrogen high-pressure sealed reactor being carried out the air-tightness affirmation again, under normal pressure, heat temperature raising, keep 190 ℃ of reaction temperatures, stirring reaction finished after 4 hours, stopped heating.
3, stir nature and cool to room temperature, open reactor, draw off liquid material in the still, analyze liquid material with gas chromatograph and form.The conversion ratio of dimethyl carbonate is 98.5%, and the selectivity of catalyst p-methylphenyl carbonic ester (MPC), diphenyl carbonate (DPC) is respectively 56.5% and 42.0%.
Embodiment 2:
1, takes by weighing sodium molybdate (Na
2MoO
4H
2O) 20.0 grams (containing about 7.9 grams of molybdenum) are dissolved in the distilled water, are made into the solution of 40% (mass percent); Then its 20% (percent by volume) salpeter solution with preparation is mixed with cocurrent process, simultaneously, drip 45ml isopropyl titanate (about 6.8 grams of titaniferous), stir precipitation, vacuum filtration; With gained sediment or gel in baking oven 90-120 ℃ dry 12 hours down; With dried sediment in Muffle furnace in 500 ℃ of roasting temperatures 5 hours, take out and promptly get molybdenum-titanium O composite metallic oxide catalyst.
2, take by weighing the autoclave that 80.0 gram phenylacetates (about 0.60mol), 25.0 gram dimethyl carbonates (about 0.28mol) and 3.0 restraints molybdenum-titanium compound oxide catalyst fully join the subsidiary intelligent constant-temperature controller of 250ml, seal with securing member, after with nitrogen high-pressure sealed reactor being carried out the air-tightness affirmation again, under normal pressure, heat temperature raising, keep 180 ℃ of reaction temperatures, stirring reaction finished after 3 hours, stopped heating.
3, stir nature and cool to room temperature, open reactor, draw off liquid material in the still, analyze liquid material with gas chromatograph and form.The conversion ratio of dimethyl carbonate is 80.0%, and the selectivity of catalyst p-methylphenyl carbonic ester (MPC), diphenyl carbonate (DPC) is respectively 57.0% and 39.5%.
Embodiment 3:
1, takes by weighing ammonium dimolybdate ((NH
4)
2Mo
2O
7) 20.0 grams (containing about 11.0 grams of molybdenum), be dissolved in the distilled water, be made into the solution of 50% (mass percent); Then with its 20% (percent by volume) oxalic acid solution, 30% (mass percent) titanyl sulfate (TiOSO with preparation
4H
2O) solution (about 1.1 grams of titaniferous) mixes with cocurrent process, stirs precipitation, vacuum filtration; With the gained sediment in baking oven 90-120 ℃ dry 12 hours down; With dried sediment or gel in Muffle furnace in 500 ℃ of roasting temperatures 3 hours, take out and promptly get molybdenum-titanium O composite metallic oxide catalyst.
2, take by weighing the autoclave that 110.0 gram phenylacetates (about 0.80mol), 36.0 gram dimethyl carbonates (about 0.40mol) and 8.0 restraints molybdenum-titanium compound oxide catalyst fully join the subsidiary intelligent constant-temperature controller of 250ml, seal with securing member, after with nitrogen high-pressure sealed reactor being carried out the air-tightness affirmation again, under normal pressure, heat temperature raising, keep 180 ℃ of reaction temperatures, stirring reaction finished after 6 hours, stopped heating.
3, stir nature and cool to room temperature, open reactor, draw off liquid material in the still, analyze liquid material with gas chromatograph and form.The conversion ratio of dimethyl carbonate is 70.0%, catalyst p-methylphenyl carbonic ester (MPC), and the selectivity of diphenyl carbonate (DPC) is respectively 55.0% and 42.0%.
Embodiment 4:
1, takes by weighing 20.0 gram ammonium molybdate ((NH
4)
6Mo
7O
24H
2O) (contain about 11 grams of molybdenum) and be dissolved in the distilled water, be made into the solution of 30% (mass percent), 30% (percent by volume) citric acid solution that will prepare then precipitates with cocurrent process mixing stirring, and vacuum filtration is standby; Measure 40ml tetrabutyl titanate (about 5.6 grams of titaniferous) and dropwise add in the distilled water, stirring, hydrolytic precipitation, vacuum filtration, standby.With above-mentioned two kinds of standby sediments or gel in baking oven 90-120 ℃ dry 12 hours down; Fully ground and mixed is even in mortar with dried sediment, then in Muffle furnace in 600 ℃ of roasting temperatures 5 hours, take out and promptly get molybdenum-titanium O composite metallic oxide catalyst.
2, take by weighing the autoclave that 110.0 gram phenylacetates (about 0.80mol), 36.0 gram dimethyl carbonates (about 0.40mol) and 6.0 restraints molybdenum-titanium compound oxide catalyst fully join the subsidiary intelligent constant-temperature controller of 250ml, seal with securing member, after with nitrogen high-pressure sealed reactor being carried out the air-tightness affirmation again, under normal pressure, heat temperature raising, keep 180 ℃ of reaction temperatures, stirring reaction finished after 2 hours, stopped heating.
3, stir nature and cool to room temperature, open reactor, draw off liquid material in the still, analyze liquid material with gas chromatograph and form.The conversion ratio of dimethyl carbonate is 50.0%, catalyst p-methylphenyl carbonic ester (MPC), and the selectivity of diphenyl carbonate (DPC) is respectively 56.0% and 40.0%.
Claims (7)
1. compound metal oxide catalyst for synthesizing diphenyl carbonate by using ester exchange is characterized in that: catalyst basic composition is molybdenum oxide and titanium oxide, wherein the weight ratio of molybdenum and titanium is: Mo: Ti=100: 10-100.
2. according to the preparation method of the described molybdenum of claim 1, titanium O composite metallic oxide catalyst, it is characterized in that: the step for preparing O composite metallic oxide catalyst with the precipitation method is as follows:
(1) the parent molybdenum compound is dissolved in the distilled water, is made into the solution of 10%-50% (mass percent);
(2) be made into the acid solution of 10%-40% (percent by volume) with a kind of in distilled water and acetic acid, hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, the citric acid or their mixture;
(3) above-mentioned two kinds of solution are mixed with cocurrent process, add organic titanic compound Ti (OR) 4 simultaneously, stir, precipitation, vacuum filtration;
(4) with the gained sediment in baking oven 90-120 ℃ dry 12 hours down;
(5) with dried sediment or gel in Muffle furnace in 300-600 ℃ of roasting temperature 3-8 hour, take out and promptly make O composite metallic oxide catalyst.
3. according to the preparation method of the described O composite metallic oxide catalyst of claim 2, it is characterized in that: described parent molybdenum compound is molybdic acid, ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate, sodium molybdate, potassium molybdate etc.
4. according to the preparation method of the described O composite metallic oxide catalyst of claim 2, it is characterized in that: R is a carbon number smaller or equal to 4 alkyl substituent among described organic titanic compound Ti (OR) 4.
5. according to the preparation method of the described molybdenum of claim 1, titanium O composite metallic oxide catalyst, it is characterized in that: the step for preparing O composite metallic oxide catalyst with mechanical milling method is as follows:
(1) parent molybdenum salt is dissolved in the distilled water, is made into the solution of 10%-40% (mass percent);
(2) use distilled water and acetic acid, nitric acid, hydrochloric acid, sulfuric acid to prepare the acid solution of 10%-40% (percent by volume);
(3) above-mentioned two kinds of solution are pressed cocurrent process and mixed stirring, form molybdate compound precipitation or gel, vacuum filtration;
(4) a kind of in organic titanic compound Ti (OR) 4, halogenated titanium, titanium sulfate, Titanium Nitrate, titanium phosphate, phosphoric acid-oxygen-titanium, the titanyl sulfate or their mixture are added in the distilled water, heat up and stir, form titanium-containing compound precipitation or gel, vacuum filtration;
(5) will (3), filter back gained sediment in (4), wash respectively, drying;
(6) two kinds of change things that make in (5) are ground in mortar, mix;
(7) mixture after will grinding again in Muffle furnace in 300-600 ℃ of roasting temperature 3-8 hour, take out and promptly get molybdenum-titanium O composite metallic oxide catalyst.
6. according to the preparation method of the described O composite metallic oxide catalyst of claim 5, it is characterized in that: the parent molybdenum compound is molybdic acid, ammonium dimolybdate, ammonium tetramolybdate, ammonium heptamolybdate, sodium molybdate, potassium molybdate etc.
7. according to the preparation method of the described O composite metallic oxide catalyst of claim 5, it is characterized in that: R is alkyl, alkoxy substituent among organic titanic compound Ti (OR) 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103030351A CN101905155A (en) | 2009-06-08 | 2009-06-08 | Complex metal oxide catalyst for synthesis of diphenyl carbonate by ester exchange reaction and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103030351A CN101905155A (en) | 2009-06-08 | 2009-06-08 | Complex metal oxide catalyst for synthesis of diphenyl carbonate by ester exchange reaction and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101905155A true CN101905155A (en) | 2010-12-08 |
Family
ID=43260829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009103030351A Pending CN101905155A (en) | 2009-06-08 | 2009-06-08 | Complex metal oxide catalyst for synthesis of diphenyl carbonate by ester exchange reaction and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101905155A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801311A (en) * | 2015-04-23 | 2015-07-29 | 三明学院 | MoO3/NiO/TiO2 solid acid catalyst and preparation method thereof |
| CN104841419A (en) * | 2015-04-23 | 2015-08-19 | 三明学院 | MoO3/ZnO/TiO2 solid acid catalyst and preparation method thereof |
| CN104857967A (en) * | 2015-04-23 | 2015-08-26 | 三明学院 | Acidic oxide MoO3 / CuO / TiO2 and preparation method and application thereof |
| CN104857951A (en) * | 2015-04-23 | 2015-08-26 | 三明学院 | Preparation method of acidic oxide MoO3 / MnO / TiO2 |
| WO2018156835A1 (en) * | 2017-02-24 | 2018-08-30 | BWXT Isotope Technology Group, Inc. | Metal-molybdate and method for making the same |
| CN109678721A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | For phenol ester exchange system for the method for diphenyl carbonate |
| CN110252274A (en) * | 2019-06-14 | 2019-09-20 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | The preparation method of ester exchange synthesizing diphenyl carbonate catalyst |
| US11363709B2 (en) | 2017-02-24 | 2022-06-14 | BWXT Isotope Technology Group, Inc. | Irradiation targets for the production of radioisotopes |
| RU2795029C2 (en) * | 2017-02-24 | 2023-04-27 | БВКсТ ИЗОТОП ТЕКНОЛОДЖИ ГРУП, ИНК. | Metal-molybdate and method for its production |
-
2009
- 2009-06-08 CN CN2009103030351A patent/CN101905155A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| 余新武等: "纳米TiO2-MoO3的制备及对甲基红的催化降解", 《功能材料》 * |
| 王智民等: "MoO3-V205，MoO3-TiO2(锐钛矿型),moo3-wo3和moo3-zro2界面过渡层上的双向分散阈值及非单层分散模型", 《催化学报》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104801311A (en) * | 2015-04-23 | 2015-07-29 | 三明学院 | MoO3/NiO/TiO2 solid acid catalyst and preparation method thereof |
| CN104841419A (en) * | 2015-04-23 | 2015-08-19 | 三明学院 | MoO3/ZnO/TiO2 solid acid catalyst and preparation method thereof |
| CN104857967A (en) * | 2015-04-23 | 2015-08-26 | 三明学院 | Acidic oxide MoO3 / CuO / TiO2 and preparation method and application thereof |
| CN104857951A (en) * | 2015-04-23 | 2015-08-26 | 三明学院 | Preparation method of acidic oxide MoO3 / MnO / TiO2 |
| CN104801311B (en) * | 2015-04-23 | 2017-12-08 | 三明学院 | MoO3/NiO/TiO2Solid acid catalyst and preparation method thereof |
| US11286172B2 (en) | 2017-02-24 | 2022-03-29 | BWXT Isotope Technology Group, Inc. | Metal-molybdate and method for making the same |
| WO2018156835A1 (en) * | 2017-02-24 | 2018-08-30 | BWXT Isotope Technology Group, Inc. | Metal-molybdate and method for making the same |
| US11363709B2 (en) | 2017-02-24 | 2022-06-14 | BWXT Isotope Technology Group, Inc. | Irradiation targets for the production of radioisotopes |
| RU2795029C2 (en) * | 2017-02-24 | 2023-04-27 | БВКсТ ИЗОТОП ТЕКНОЛОДЖИ ГРУП, ИНК. | Metal-molybdate and method for its production |
| US11974386B2 (en) | 2017-02-24 | 2024-04-30 | BWXT Isotope Technology Group, Inc. | Irradiation targets for the production of radioisotopes |
| CN109678721A (en) * | 2017-10-19 | 2019-04-26 | 中国石油化工股份有限公司 | For phenol ester exchange system for the method for diphenyl carbonate |
| CN109678721B (en) * | 2017-10-19 | 2021-08-03 | 中国石油化工股份有限公司 | Method for preparing diphenyl carbonate by phenol ester exchange |
| CN110252274A (en) * | 2019-06-14 | 2019-09-20 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | The preparation method of ester exchange synthesizing diphenyl carbonate catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101905155A (en) | Complex metal oxide catalyst for synthesis of diphenyl carbonate by ester exchange reaction and preparation method thereof | |
| CN103140287B (en) | Use the ester exchange method of salt-mixture acetylacetonate catalyst | |
| CN101492528B (en) | Method for synthesis of alicyclic epoxy resin with catalysis of solid supported heteropoly acid catalyst | |
| CN104447312B (en) | A kind of method of Synthesis of dimethyl carbonate | |
| CN112138708B (en) | Solid acid catalyst and preparation method and application thereof | |
| CN104383951A (en) | Catalyst for synthesis of linear carbonate by virtue of transesterification of cyclic carbonate and alcohol and preparing method of catalyst | |
| CN101774911A (en) | Catalyzing method of synthesizing diphenyl carbonate through ester exchange reaction | |
| CN102974370B (en) | Solid acid catalyst and use thereof | |
| CN101628874A (en) | Method for synthesizing diphenyl carbonate through ester exchange reaction of dimethyl carbonate and phenylethyl acetate | |
| CN112844372A (en) | Oxygen vacancy-containing bismuth molybdate thermal catalyst and preparation method and application thereof | |
| CN105396613A (en) | Composite mesoporous molecular sieve solid superacid and preparation method thereof | |
| CN110152704B (en) | Metal-free solid catalyst for synthesizing linear carbonate and preparation method thereof | |
| CN109678713B (en) | Method for preparing diphenyl carbonate by ester exchange | |
| CN101468315B (en) | Method for preparing multiphase catalyst for exchange reaction of dimethyl carbonate and phenol ester | |
| CN102675115B (en) | Method for synthesizing diphenyl carbonate from dimethyl carbonate | |
| CN101851154B (en) | Improved method for producing 2-alkylene alicyclic ketone | |
| CN104801311A (en) | MoO3/NiO/TiO2 solid acid catalyst and preparation method thereof | |
| CN104437607B (en) | Stanniferous molecular sieve catalyst and the using method of ethylene glycol is prepared for ethylene oxide hydration | |
| CN108586193A (en) | A method of preparing 1,3-PD using 3- methoxy methyl propionates | |
| CN106117041B (en) | A kind of synthetic method of isooctyl acid bismuth | |
| CN108727192B (en) | Preparation method of diphenyl carbonate compound | |
| CN109772419B (en) | Preparation method for constructing carbon nitride-based ultrathin nanosheet composite material in confined space | |
| CN112439428B (en) | Preparation method and application of solid acid catalyst | |
| CN106076304A (en) | Transesterification supported titanium2the preparation method of catalyst | |
| CN109265344B (en) | Preparation method of diphenyl carbonate compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20101208 |