CN105732361A - An anhydride producing method - Google Patents
An anhydride producing method Download PDFInfo
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- CN105732361A CN105732361A CN201410758255.4A CN201410758255A CN105732361A CN 105732361 A CN105732361 A CN 105732361A CN 201410758255 A CN201410758255 A CN 201410758255A CN 105732361 A CN105732361 A CN 105732361A
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Abstract
An anhydride producing method is disclosed. The method includes oxidizing a C2-C7 alcohol or a C2-C7 aldehyde under the existence of a catalyst and an oxidant to obtain an anhydride, wherein the reaction pressure is atmospheric pressure, the temperature is 50-200 DEG C, the hourly space velocity is 0.5-100 h<-1>, the catalyst is a supported type Pd catalyst and the oxidant is oxygen or air. The method adopts the oxygen as the oxidant, and achieves high-selectivity conversion of the alcohol or the aldehyde to the anhydride through an oxidizing manner. Anhydride selectivity is 10-85%. A substrate conversion rate is 10-100%. The yield of the anhydride is 10-85%. The method does not need a high reaction temperature and can be performed at room temperature or a temperature close to room temperature, thus saving a large amount of energy. The method is low in equipment requirement, low in investment, simple in reaction system and easy in industrialization. The catalyst is long in service lifetime and free of loss.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to a kind of method producing anhydride.
Background technology
Acetic anhydride is as a kind of important Organic Chemicals, and annual production, up to tons up to a million, is mainly used to acetylation of cellulose and prepares acetate fiber.Acetate fiber and acetic starch can be applicable in the fields such as coating, binding agent, cigarette filter, and degradation plastic.Acetic anhydride, as acylating reagent, is widely used in organic synthesis, as prepared aspirin with salicylism reaction, prepares glycerol acetate with glycerine reaction, and in other reaction.
Industrially the preparation method of acetic anhydride mainly has three kinds at present, acetaldehyde oxidation, ketene process and methyl acetate carbonylation method.Acetaldehyde oxidation is to be catalyst with cobalt acetate and copper acetate, air as oxidant, oxidizing acetaldehyde under 329K, through peracetic acid intermediate, be synthesized with another molecules of acetaldehyde and obtain.Ketenes rule is with acetic acid for raw material, and under triethyl phosphate catalysis, 1023K cracking obtains the intermediate of ketenes, and prepares with another molecule acetic acidreaction.There is the problems such as power consumption and cost due to both approaches, people have tried to the synthetic route that exploitation is new.Methyl acetate carbonylation is then react production under rhodium base catalyst with carbon monoxide and methyl acetate to obtain, and energy consumption of reaction is low, and product purity is high.But the CO (carbon monoxide converter) gas used in this technique has certain toxicity and danger.Additionally, the industrial making method of three of the above acetic anhydride all adopts homogeneous catalysis system, thus there is the product problem that separate more difficult with catalyst.
Summary of the invention
It is an object of the invention to provide a kind of method producing anhydride.
The method of production anhydride provided by the invention, comprises the steps:
Under catalyst and oxidant existent condition, the aldehyde of the alcohol of C2-C7 or C2-C7 is carried out oxidation reaction, react complete and obtain anhydride.
In said method, the alcohol of described C2-C7 concretely ethanol or propanol；
The aldehyde of described C2-C7 concretely acetaldehyde or propionic aldehyde.
Described anhydride concretely acetic anhydride or propionic andydride.
When the aldehyde that alcohol is ethanol or C2-C7 of C2-C7 used is acetaldehyde, gained anhydride is acetic anhydride；
When the aldehyde that alcohol is propanol or C2-C7 of C2-C7 used is propionic aldehyde, gained anhydride is propionic andydride；
In described oxidation step, reaction pressure is 1 atmospheric pressure；Reaction temperature is 50-200 DEG C, is specially 120 DEG C；Volume space velocity is 0.5h-1-100h-1, it is specially 40h-1；
Described catalyst is Supported Pd-Catalyst；The Supported Pd-Catalyst that various conventional methods obtain is all applicable, as being the Supported Pd-Catalyst prepared by wet impregnation method；
Wherein, carrier is oxide or activated carbon；
Described oxide is chosen in particular from least one in zirconium dioxide, silicon dioxide, aluminium oxide, ceria and titanium dioxide；
The mass ratio of Pd and described carrier is 2-15:100, is specially 10:100 or 15:100.
Described oxidant is oxygen or air.
The alcohol of described C2-C7 or the aldehyde of C2-C7 account for the 1%-15% of the total dividing potential drop of reaction gas in reaction system, are specially 3%.
The present invention passes through oxidative pathway, utilize oxygen or air as oxidant, Supported Pd-Catalyst is as heterogeneous catalyst, the anhydride of correspondence is obtained through peroxidating alcohol or aldehyde, achieve alcohol or aldehyde by the mode of oxidizing high selective conversion to anhydride, anhydride selectivity reaches 10-85%, and substrate conversion efficiency reaches 10-100%, and the productivity of anhydride reaches 10-85%.Can being converted by ethanol 100%, the selectivity of acetic anhydride is 50-80%, and acetic anhydride productivity is 50-80%, it is possible to converted by propanol 100%, and propionic andydride selectivity is 55-85%, and propionic andydride productivity is 55-85%.Adopted heterogeneous catalytic system, it is easy to catalyst separates with product, it is not necessary to higher reaction temperature, can occur when at room temperature or close to room temperature, save the substantial amounts of energy；The inventive method carries out under the oxygen existent condition of normal pressure, and the requirement for equipment is low, invests little；The inventive method reaction system is simple, it is easy to industrialization, and catalyst life is long, without running off.
Accompanying drawing explanation
Fig. 1 is the GC-MS spectrogram of embodiment 1 products therefrom.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following example.Described method is conventional method if no special instructions.Described normal pressure if no special instructions, is 1 atmospheric pressure.Described raw material all can obtain from open commercial sources if no special instructions, and wherein, oxygen, nitrogen are the high-purity gas of Hai Pu company；Supported catalyst used carrier is that Sigma buys；Preparing the raw material used by Pd is that traditional Chinese medicines are bought；The analytical pure that reactant (ethanol, propionic aldehyde, propanol) is traditional Chinese medicines, acetaldehyde is prepared by paraldehydum acidolysis.
In following embodiment, the preparation method of Supported Pd-Catalyst used is as follows:
By PdCl2Dissolve with concentrated hydrochloric acid, add isopyknic carrier, concussion dipping, dry and roasting under air atmosphere at 500 DEG C, obtain Supported Pd-Catalyst.Used carrier is oxide or activated carbon；Oxide is specifically selected from least one in zirconium dioxide, silicon dioxide, aluminium oxide, ceria and titanium dioxide；The mass ratio of Pd and carrier is 2-15:100.
In following embodiment, the conversion ratio of ethanol or propanol all calculates according to equation below:
Conversion ratio=(total amount of substance of the amount/reactant of 1 unreacted reactant species) × 100%
All products can be amounted to into according to C atomic number the inversion quantity of corresponding reactant, for instance 1mol methane is converted by 0.5mol ethanol molecule and obtains, and 1mol acetic anhydride has 2mol ethanol conversion to obtain.
The selectivity of acetic anhydride or propionic andydride all calculates according to equation below:
Selectivity=(reactant amounting to amount of substance/conversion of target anhydride always amounts to amount of substance) × 100%
All embodiment products therefroms detect each through GC-MS, it is determined that the species ownership of product, determine the productivity of product with the standard curve method in GC.
Embodiment 1, oxidation of ethanol are directly synthesized acetic anhydride
1 atmospheric pressure, 120 DEG C, 3% ethanol/air (ethanol accounts for the 3% of the total dividing potential drop of reaction gas), volume space velocity is 40h-1, catalyst is Supported Pd-Catalyst Pd/ZrO2, Pd and ZrO2Mass ratio be 10:100, it is shown that ethanolic moiety is converted into acetic anhydride, the conversion ratio of ethanol is 100%, and the selectivity of acetic anhydride is 50%, and acetic anhydride productivity is 50%.
Utilizing GC-MS to determine the structure of products therefrom, gained spectrogram is as shown in Figure 1.As seen from the figure, products therefrom is acetic anhydride.
Embodiment 2, oxidation of acetaldehyde are directly synthesized acetic anhydride
1 atmospheric pressure, 120 DEG C, 3% acetaldehyde/air (acetaldehyde accounts for the 3% of the total dividing potential drop of reaction gas), volume space velocity is 40h-1, catalyst is Supported Pd-Catalyst Pd/ZrO2, Pd and ZrO2Mass ratio be 10:100, it is shown that acetaldehyde is partially converted into acetic anhydride, the conversion ratio of acetaldehyde is 100%, and the selectivity of acetic anhydride is 80%, and acetic anhydride productivity is 80%.
The oxidation of embodiment 3, propionic aldehyde is directly synthesized propionic andydride
1 atmospheric pressure, 120 DEG C, 3% propionic aldehyde/air (propionic aldehyde accounts for the 3% of the total dividing potential drop of reaction gas), air speed is 40h-1, catalyst is Supported Pd-Catalyst Pd/ZrO2, Pd and ZrO2Mass ratio be 10:100, it is shown that propionic aldehyde is partially converted into propionic andydride, the conversion ratio of propionic aldehyde is 100%, and the selectivity of propionic andydride is 85%, and propionic andydride productivity is 85%.
The oxidation of embodiment 4, propanol is directly synthesized propionic andydride
1 atmospheric pressure, 120 DEG C, 3% propanol/air (propanol accounts for the 3% of the total dividing potential drop of reaction gas), volume space velocity is 40h-1, catalyst is Supported Pd-Catalyst Pd/ZrO2, Pd and ZrO2Mass ratio be 10:100, it is shown that propanol is partially converted into propionic andydride, the conversion ratio of propanol is 100%, and the selectivity of anhydride is 55%, and propionic andydride productivity is 55%.
Embodiment 5, oxidation of ethanol are directly synthesized acetic anhydride
1 atmospheric pressure, 120 DEG C, 3% ethanol/air, volume space velocity is 40h-1, catalyst is Supported Pd-Catalyst Pd/SiO2, Pd and SiO2Mass ratio be 10:100, it is shown that ethanolic moiety is converted into acetic anhydride, the conversion ratio of ethanol is 95%, and the selectivity of acetic anhydride is 40%, and acetic anhydride productivity is 38%.
Embodiment 6, oxidation of ethanol are directly synthesized acetic anhydride
1 atmospheric pressure, 120 DEG C, 3% ethanol/air, air speed is 40h-1, catalyst is Supported Pd-Catalyst Pd/Al2O3, Pd and Al2O3Mass ratio be 10:100, it is shown that ethanolic moiety is converted into acetic anhydride, the conversion ratio of ethanol is 90%, and the selectivity of acetic anhydride is 41%, and acetic anhydride productivity is 36%.
Embodiment 7, oxidation of ethanol are directly synthesized acetic anhydride
1 atmospheric pressure, 120 DEG C, 3% ethanol/air, volume space velocity is 40h-1, catalyst is Supported Pd-Catalyst Pd/CeO2, Pd and CeO2Mass ratio be 10:100, it is shown that ethanolic moiety is converted into acetic anhydride, the conversion ratio of ethanol is 78%, and the selectivity of acetic anhydride is 30%, and acetic anhydride productivity is 23%.
Embodiment 8, oxidation of ethanol are directly synthesized acetic anhydride
1 atmospheric pressure, 120 DEG C, 3% ethanol/air, volume space velocity is 40h-1, catalyst is Supported Pd-Catalyst Pd/TiO2, Pd and TiO2Mass ratio be 10:100, it is shown that ethanolic moiety is converted into acetic anhydride, the conversion ratio of ethanol is 50%, and the selectivity of acetic anhydride is 14%, and acetic anhydride productivity is 7%.
Embodiment 9, oxidation of ethanol are directly synthesized acetic anhydride
1 atmospheric pressure, 120 DEG C, 3% ethanol/air, volume space velocity is 40h-1, catalyst is Supported Pd-Catalyst Pd/C (activated carbon), and the mass ratio of Pd and C is 10:100, it is shown that ethanolic moiety is converted into acetic anhydride, the conversion ratio of ethanol is 20%, and the selectivity of acetic anhydride is 10%, and acetic anhydride productivity is 2%.
Embodiment 10, oxidation of ethanol are directly synthesized acetic anhydride
1 atmospheric pressure, 120 DEG C, 3% ethanol/air, volume space velocity is 40h-1, catalyst is Supported Pd-Catalyst Pd/ZrO2, Pd and ZrO2Mass ratio be 2:100, it is shown that ethanolic moiety is converted into acetic anhydride, the conversion ratio of ethanol is 60%, and the selectivity of acetic anhydride is 20%, and acetic anhydride productivity is 12%.
Embodiment 11, oxidation of ethanol are directly synthesized acetic anhydride
1 atmospheric pressure, 120 DEG C, 3% ethanol/air, volume space velocity is 40h-1, catalyst is Supported Pd-Catalyst Pd/ZrO2, Pd and ZrO2Mass ratio be 15:100, it is shown that ethanolic moiety is converted into acetic anhydride, the conversion ratio of ethanol is 100%, and the selectivity of acetic anhydride is 52%, and acetic anhydride productivity is 52%.
Claims (10)
1. the method producing anhydride, comprises the steps:
Under catalyst and oxidant existent condition, the aldehyde of the alcohol of C2-C7 or C2-C7 is carried out oxidation reaction, react complete and obtain anhydride.
2. method according to claim 1, it is characterised in that: the alcohol of described C2-C7 is ethanol or propanol；
The aldehyde of described C2-C7 is acetaldehyde or propionic aldehyde.
3. method according to claim 1 and 2, it is characterised in that: in described oxidation step, reaction pressure is 1 atmospheric pressure.
4. according to described method arbitrary in claim 1-3, it is characterised in that: in described oxidation step, reaction temperature is 50 DEG C-200 DEG C.
5. according to described method arbitrary in claim 1-4, it is characterised in that: in described oxidation step, volume space velocity is 0.5h-1-100h-1。
6. according to described method arbitrary in claim 1-5, it is characterised in that: described catalyst is Supported Pd-Catalyst, is made up of Pd and carrier；
Wherein, described carrier is oxide or activated carbon.
7. method according to claim 6, it is characterised in that: described oxide at least one in zirconium dioxide, silicon dioxide, aluminium oxide, ceria and titanium dioxide.
8. the method according to claim 6 or 7, it is characterised in that: the mass ratio of Pd and described carrier is 2-15:100.
9. according to described method arbitrary in claim 1-8, it is characterised in that: described oxidant is oxygen or air.
10. according to described method arbitrary in claim 1-9, it is characterised in that: the alcohol of described C2-C7 or the aldehyde of C2-C7 account for the 1%-15% of the total dividing potential drop of reaction gas in reaction system.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110449151A (en) * | 2019-09-03 | 2019-11-15 | 福州大学 | A kind of loading type Pd/ZrO2The preparation method and applications of catalyst |
| CN114072429A (en) * | 2019-05-24 | 2022-02-18 | 伊士曼化工公司 | Recovery of constituent cellulose ester |
Citations (1)
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| CN1669646A (en) * | 2004-12-31 | 2005-09-21 | 厦门大学 | Palladium-containing solid catalyst for synthesizing aldehyde or ketone and preparation process thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1669646A (en) * | 2004-12-31 | 2005-09-21 | 厦门大学 | Palladium-containing solid catalyst for synthesizing aldehyde or ketone and preparation process thereof |
Non-Patent Citations (3)
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| CHERNYSHEVA, T. V. ET AL.: "《Reactions of palladium(I) carbonyl acetate cluster with alcohols》", 《IZVESTIYA AKADEMII NAUK, SERIYA KHIMICHESKAYA》 * |
| M.K.STARCHEVSKII ET AL.: "《Ethanol oxidation catalyzed by the Pd-561 giant clusters of palladium: acetic anhydride formation》", 《KINETICS AND CATALYSIS》 * |
| Н.С. КАРАМАН ET AL.: "《Вплив стеричних факторівна селективність окиснення альдегідів С2–С6у розчинах кластеру Pd561Phen60(ОАc)180》", 《КАТАЛИЗ И НЕФТЕХИМИЯ》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114072429A (en) * | 2019-05-24 | 2022-02-18 | 伊士曼化工公司 | Recovery of constituent cellulose ester |
| CN114072429B (en) * | 2019-05-24 | 2023-12-26 | 伊士曼化工公司 | Recovery of component cellulose esters |
| CN110449151A (en) * | 2019-09-03 | 2019-11-15 | 福州大学 | A kind of loading type Pd/ZrO2The preparation method and applications of catalyst |
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