CN1701849A - Method for catalytic oxidation of saturated hydrocarbons compound - Google Patents
Method for catalytic oxidation of saturated hydrocarbons compound Download PDFInfo
- Publication number
- CN1701849A CN1701849A CN 200510070366 CN200510070366A CN1701849A CN 1701849 A CN1701849 A CN 1701849A CN 200510070366 CN200510070366 CN 200510070366 CN 200510070366 A CN200510070366 A CN 200510070366A CN 1701849 A CN1701849 A CN 1701849A
- Authority
- CN
- China
- Prior art keywords
- chitosan
- saturated hydrocarbons
- acid
- hydrocarbons compound
- reaction
- 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.)
- Granted
Links
Images
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
This invention discloses a catalytic oxidation method for saturated hydrocarbon compound, which is characterized in that, use chitose amino acid derivatives (or chitose) as ligand to prepare chitose-group metal composite as activator; in normal pressure or low pressure system, use air, O2, H2O2 or CH3COOOH as oxygen supply agent to take catalytic oxidation reaction for saturated hydrocarbon compound, then it can prepare oxidation products selected. The method of this invention has the advantage that high activity, high selectivity, easy to separate and recycle for activator, environment amity, and mild of reaction condition.
Description
Technical field
The present invention relates to a kind of method of novel saturated hydrocarbons material catalyzed oxidation.
Background technology
The selective oxidation of c h bond is the interested fields of chemists always in the stable hydrocarbon, also is open question, is because the bond energy of the c h bond of these stable hydrocarbon is higher on the one hand, is difficult to oxidation; Be because intermediate product alcohol or aldehyde that oxidation generates are more active than raw material hydrocarbon on the other hand; The easier final product carboxylic acid that further is oxidized to, very difficult highly selective obtains alcohol or aldehyde.The industrial production of saturated carbon atom oxidation at present mainly is to obtain by the stoichiometry oxidation method of high price oxygenant or the catalyzed oxidation under the High Temperature High Pressure, and chemical oxidization method exists transformation efficiency generally lower, and has very serious environmental pollution problem; Though and catalyzed oxidation can suitably improve transformation efficiency under the High Temperature High Pressure, but its harsh reaction conditions makes reaction preference relatively poor, can't prepare the alcohol aldehyde intermediate by highly selective, and there are problems such as difficult separation and recycling, large usage quantity, easy poisoning in above-mentioned catalyzer.Therefore, all there is very important meaning in the novel method of searching high reactivity, highly selective, environmental friendliness, the easily separated recovery of catalyzer to the industrial applications of promotes oxidn reaction.
Summary of the invention
The method that the purpose of this invention is to provide a kind of saturated hydrocarbons compound catalyzed oxidation, it is that chitosan is carried out modification produces the chitosan derivatives with amino acid structure, with the gained derivative or directly be that part and multiple metal ion (transition metal, rare earth metal) carry out complexing with the chitosan, produce chitosan-based macromolecule metal analogue enztme, with air, the O of gained macromolecule metal analogue enztme catalysis cleaning under normal pressure or low pressure, lesser temps with enzymatic structure
2, H
2O
2Or CH
3COOOH carries out catalytic oxidation to saturated hydrocarbons material alkane, aromatic hydrocarbons and saturated alcohol, selectivity preparation alcohol, aldehyde intermediate product.
The present invention is achieved in that oxoethanoic acid and chitosan is carried out the Schiff reaction, generates chitosan oxoethanoic acid imines, utilizes the carboxyl of chitosan oxoethanoic acid imines and amino acid to carry out acylation reaction, thereby obtains to have the chitosan derivatives of amino acid structure; Perhaps amino acid is at dense H
2SO
4Catalysis is descended directly and chitosan carries out acylation reaction, preparation amino of chitosan acid derivative; With gained chitosan derivatives and transition metal ion (Cu, Ni, Co, Mn, Fe, Zn, Ti, Cr, La, Pb, Rh, Pd+2 ,+3 valency ions), or rare earth ion (Y, La, Pr, Nd, Er+3 valency ions) effect forms high molecular metal complex, with air, the O of gained metal complexes catalysis cleaning under normal pressure or low pressure, lesser temps
2, H
2O
2Or CH
3COOOH carries out catalytic oxidation to saturated hydrocarbons material alkane, aromatic hydrocarbons and saturated alcohol, promptly optionally prepares oxidation products.
The method of a kind of saturated hydrocarbons compound catalyzed oxidation provided by the present invention exists high reactivity, highly selective, and catalyzer is easy to the characteristics of Separation and Recovery, environmental friendliness, reaction conditions gentleness.
Description of drawings
Fig. 1 is the process flow sheet of the method for a kind of saturated hydrocarbons compound catalyzed oxidation of the present invention.
Embodiment
Further the present invention will be described below in conjunction with accompanying drawing
1, the chitosan with deacetylation 60-100% is raw material distilled water swelling 2-24h, add the 5-30% glyoxylic acid solution, reaction 2-72h, filter, use distilled water wash, dry chitosan oxoethanoic acid imines, again with chitosan oxoethanoic acid imines and amino acid ester at 15-80 ℃, be acidifying catalyzed reaction 1-72h under the condition of 1-6 in the pH value, the amino of chitosan acid derivative; Described acidulated condition is meant H
2SO
4, HCl, acetic acid, phosphoric acid.Amino of chitosan acid derivative preparation also can be by chitosan directly and amino acid, is acidifying catalyzed reaction 1-48h under the condition of 1-6 in pH value, must the amino of chitosan acid derivative, and described acidulated condition is meant H
2SO
4, HCl, acetic acid.
2, with the amino of chitosan acid derivative or directly be part with the chitosan, homogeneous phase or inhomogeneous reaction under 15-50 ℃ the temperature with transition metal ion or rare earth ion ligand complex 2-24h, prepare corresponding chitosan-based metal complexes.Described homogeneous phase is meant water, acetic acid phase or hydrochloric acid phase; Described transition metal ion is meant Cu, Ni, and Co, Mn, Fe, Zn, Ti, Cr, La, Pb, Rh, Pd+2 ,+3 valency ions; Described rare earth ion is meant Y, La, Pr, Nd, Er's+3 valency ions.
3, be catalyzer with the chitosan-based metal complexes of gained, normal pressure or pressure between the 0.1-3Mpa, temperature is between 15-200 ℃, with air, the O of cleaning
2, H
2O
2Or CH
3COOOH is an oxygenate, and saturated hydrocarbons compound is carried out catalytic oxidation, and reaction 2-72h promptly optionally prepares alcohol, aldehyde intermediate product; Described saturated hydrocarbons compound is meant alkane, aromatic hydrocarbons and saturated alcohol.
Embodiment one:
With the chitosan is part, and under the normal temperature and pressure, water is solvent, with FeSO
4Reactant aqueous solution 5h gets chitosan-Fe (II) title complex (CTS-Fe).Weighing CTS-Fe 0.02g adds and is equipped with in the flask of 20mL toluene, adds 10mL CH again
3COOOH, normal pressure, 72 ℃, reaction 13h gets the organic phase gas chromatographic detection, pure aldehyde 95% in the product, aldehyde is about 90%, and the toluene per pass conversion is 20%.
Embodiment two:
In the flask of the THF that 50mL is housed, add 10mLH
2SO
4Be catalyzer, 10g L-methionine(Met), 6g chitosan successively add wherein, and reaction 48h filters under 50 ℃ of stirrings, and distilled water wash is extremely neutral, the dry chitosan methionine(Met) derivative that gets.Under the normal temperature and pressure, water is solvent, chitosan methionine(Met) derivative and Cu (OAc)
2Carry out complex reaction, reaction 5h filters, and distilled water wash is the metal ion of complexing not, the dry chitosan-based metal complexes (CTS-cys-Cu) that gets.Get 0.04g CTS-cys-Cu at normal pressure, seethe with excitement, reflux and stir down, reaction 24h, catalysis 10mL toluene oxidation gets phenyl aldehyde, selectivity 90%, once through yield 10%.
Claims (8)
1, a kind of method of saturated hydrocarbons compound catalyzed oxidation is characterized in that:
1) chitosan with deacetylation 60-100% is raw material distilled water swelling 2-24h, add the 5-30% glyoxylic acid solution, reaction 2-72h, filter, use distilled water wash, dry chitosan oxoethanoic acid imines, again with chitosan oxoethanoic acid imines and amino acid ester at 15-80 ℃, be acidifying catalyzed reaction 1-72h under the condition of 1-6 in the pH value, the amino of chitosan acid derivative;
2) with the amino of chitosan acid derivative or directly be part with the chitosan, homogeneous phase or inhomogeneous reaction under 15-50 ℃ the temperature with transition metal ion or rare earth ion ligand complex 2-24h, prepare corresponding chitosan-based metal complexes;
3) be catalyzer with the chitosan-based metal complexes of gained, normal pressure or pressure between the 0.1-3Mpa, temperature is between 15-200 ℃, with air, the O of cleaning
2, H
2O
2Or CH
3COOOH is an oxygenate, and saturated hydrocarbons compound is carried out catalytic oxidation, and reaction 2-72h promptly optionally prepares alcohol, aldehyde intermediate product.
2, according to the method for the said saturated hydrocarbons compound catalyzed oxidation of claim 1, it is characterized in that: described acidulated condition is meant H
2SO
4, HCl, acetic acid, phosphoric acid.
3, according to the method for the said saturated hydrocarbons compound catalyzed oxidation of claim 1, it is characterized in that: the preparation of described amino of chitosan acid derivative also can be by chitosan directly and amino acid, is acidifying catalyzed reaction 1-48h under the condition of 1-6 in the pH value.
4, according to the method for the said saturated hydrocarbons compound catalyzed oxidation of claim 3, it is characterized in that: described acidulated condition is meant H
2SO
4, HCl, acetic acid.
5, according to the method for the said saturated hydrocarbons compound catalyzed oxidation of claim 1, it is characterized in that: described homogeneous phase is meant water, acetic acid phase or hydrochloric acid phase.
6, according to the method for the said saturated hydrocarbons compound catalyzed oxidation of claim 1, it is characterized in that: described transition metal ion is meant Cu, Ni, and Co, Mn, Fe, Zn, Ti, Cr, La, Pb, Rh, Pd+2 ,+3 valency ions.
7, according to the method for the said saturated hydrocarbons compound catalyzed oxidation of claim 1, it is characterized in that: described rare earth ion be meant Y, La, Pr, Nd, Er+3 valency ions.
8, according to the method for the said saturated hydrocarbons compound catalyzed oxidation of claim 1, it is characterized in that: described saturated hydrocarbons compound is meant alkane, aromatic hydrocarbons and saturated alcohol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100703667A CN100484629C (en) | 2005-04-30 | 2005-04-30 | Method for catalytic oxidation of saturated hydrocarbons compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100703667A CN100484629C (en) | 2005-04-30 | 2005-04-30 | Method for catalytic oxidation of saturated hydrocarbons compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1701849A true CN1701849A (en) | 2005-11-30 |
| CN100484629C CN100484629C (en) | 2009-05-06 |
Family
ID=35631913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100703667A Expired - Fee Related CN100484629C (en) | 2005-04-30 | 2005-04-30 | Method for catalytic oxidation of saturated hydrocarbons compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100484629C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8119780B2 (en) | 2006-06-02 | 2012-02-21 | Synedgen, Inc. | Chitosan-derivative compounds and methods of controlling microbial populations |
| CN103483469A (en) * | 2013-09-26 | 2014-01-01 | 上海大学 | Preparation method for water-soluble chitosan |
| CN108299199A (en) * | 2018-02-07 | 2018-07-20 | 兄弟科技股份有限公司 | A kind of preparation method of edible spices vanillic aldehyde |
| CN108569754A (en) * | 2018-05-07 | 2018-09-25 | 北京化工大学 | A kind of environmentally friendly sewage-treating agent and its application method and application |
-
2005
- 2005-04-30 CN CNB2005100703667A patent/CN100484629C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8119780B2 (en) | 2006-06-02 | 2012-02-21 | Synedgen, Inc. | Chitosan-derivative compounds and methods of controlling microbial populations |
| US8658775B2 (en) | 2006-06-02 | 2014-02-25 | Shenda Baker | Chitosan-derivative compounds and methods of controlling microbial populations |
| US9029351B2 (en) | 2006-06-02 | 2015-05-12 | Synedgen, Inc. | Chitosan-derivative compounds and methods of controlling microbial populations |
| US9732164B2 (en) | 2006-06-02 | 2017-08-15 | Synedgen, Inc. | Chitosan-derivative compounds and methods of controlling microbial populations |
| US10494451B2 (en) | 2006-06-02 | 2019-12-03 | Synedgen, Inc. | Chitosan-derivative compounds and methods of controlling microbial populations |
| CN103483469A (en) * | 2013-09-26 | 2014-01-01 | 上海大学 | Preparation method for water-soluble chitosan |
| CN108299199A (en) * | 2018-02-07 | 2018-07-20 | 兄弟科技股份有限公司 | A kind of preparation method of edible spices vanillic aldehyde |
| CN108299199B (en) * | 2018-02-07 | 2020-12-22 | 兄弟科技股份有限公司 | Preparation method of edible spice vanillin |
| CN108569754A (en) * | 2018-05-07 | 2018-09-25 | 北京化工大学 | A kind of environmentally friendly sewage-treating agent and its application method and application |
| CN108569754B (en) * | 2018-05-07 | 2020-06-09 | 北京化工大学 | Environment-friendly sewage treatment agent and use method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100484629C (en) | 2009-05-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101544548B (en) | Method for preparing aldehydes or ketones by oxidizing alcohols with oxygen | |
| CN103288596B (en) | A kind of organic acid Hydrogenation is for the method for monohydroxy-alcohol or dibasic alcohol | |
| Figiel et al. | Mild aerobic oxidation of benzyl alcohols to benzaldehydes in water catalyzed by aqua-soluble multicopper (II) triethanolaminate compounds | |
| CN103691451B (en) | Catalyst for synthesizing methyl formate by virtue of gas-phase methanol carbonylation as well as preparation method and application of catalyst | |
| CN103694116B (en) | Method for synthesizing methyl formate by gas-phase carbonylation of methyl alcohol | |
| CN104177319A (en) | Method for preparing 2,5-furyldiformate | |
| CN104936940A (en) | Method for making methyl methacrylate from propionaldehyde and formaldehyde via oxidative esterification | |
| CN101906038A (en) | Method for preparing ester by catalytic oxidization of 1,3-propanediol | |
| CN1701849A (en) | Method for catalytic oxidation of saturated hydrocarbons compound | |
| CN103145545B (en) | A kind of method preparing hydroxymalonic acid for glycerol catalysis oxidation | |
| Huang et al. | An efficient oxidation of toluene over Co (II) TPP supported on chitosan using air | |
| CN104525219A (en) | Method for preparing catalyst for preparing methyl glycolate by adding hydrogen into dimethyl oxalate | |
| CN108503545B (en) | Method for preparing phenylacetate by catalytic oxidation of mandelate | |
| CN110950745B (en) | Preparation method of phenylacetaldehyde | |
| CN101157677B (en) | Method for catalytic preparation of delta-valerolactone by using supported nano-gold catalyst | |
| CN102942548B (en) | Delta-dodecalactone synthesis method | |
| CN102001931A (en) | Method for preparing adipate | |
| CN102343280A (en) | Catalyst for catalyzing oxosynthesis of acetophenone and application thereof | |
| Rajabi et al. | Highly ordered mesoporous functionalized pyridinium protic ionic liquid framework as a highly efficient catalytic system in chemoselective thioacetalization of carbonyl compounds under solvent-free conditions | |
| CN113171798B (en) | Heterogeneous iron catalyst, preparation method thereof and process for preparing 2-methyl-1, 4-naphthoquinone by catalysis | |
| CN101759536A (en) | Method for preparing parahydroxybenzaldehyde by catalytic oxidation of paracresol with metalloporphyrin | |
| CN101148406B (en) | Method for preparing carboxylic acid ester by using aldehyde, alcohol and oxidizing agent as raw material | |
| CN110538668B (en) | Heteroatom-containing nano carbon material, preparation method thereof and cyclohexane oxidation method | |
| CN101100418A (en) | Method for preparing aromatic ketone or aromatic aldehyde by selectively oxidizing alkyl arene | |
| CN109894135B (en) | Nitrogen-doped carbon black loaded palladium-bismuth alloy catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090506 Termination date: 20100430 |