CN1701849A - Method for catalytic oxidation of saturated hydrocarbons compound - Google Patents
Method for catalytic oxidation of saturated hydrocarbons compound Download PDFInfo
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- 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
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- 230000003647 oxidation Effects 0.000 title claims abstract description 24
- 229930195734 saturated hydrocarbon Natural products 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 11
- 150000001875 compounds Chemical class 0.000 title claims description 12
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
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- 239000002184 metal Substances 0.000 claims abstract description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- -1 oxoethanoic acid imines Chemical class 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 6
- 150000001413 amino acids Chemical class 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 230000006196 deacetylation Effects 0.000 claims description 2
- 238000003381 deacetylation reaction Methods 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- IZGYIFFQBZWOLJ-CKAACLRMSA-N phaseic acid Chemical compound C1C(=O)C[C@@]2(C)OC[C@]1(C)[C@@]2(O)C=CC(/C)=C\C(O)=O IZGYIFFQBZWOLJ-CKAACLRMSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 3
- 238000004140 cleaning Methods 0.000 claims 1
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- 239000003054 catalyst Substances 0.000 abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 7
- 150000003862 amino acid derivatives Chemical class 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 4
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
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- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
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- 108090000790 Enzymes Proteins 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
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- PJXKDAHSYZDMOY-UHFFFAOYSA-N 2-iminoacetaldehyde Chemical compound N=CC=O PJXKDAHSYZDMOY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FFEARJCKVFRZRR-UHFFFAOYSA-N L-Methionine Natural products CSCCC(N)C(O)=O FFEARJCKVFRZRR-UHFFFAOYSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229930195722 L-methionine Natural products 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
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- 239000007800 oxidant agent Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种饱和烃类化合物催化氧化的方法，其特征是以壳聚糖氨基酸衍生物(或壳聚糖)为配体，制备壳聚糖基金属配合物，并以所得配合物为催化剂，在常压或低压体系中，以空气、O2、H2O2或CH3COOOH为供氧剂，对饱和烃类化合物进行催化氧化反应，即可选择性地制备氧化产物。由本发明所涉及方法存在高活性、高选择性，催化剂易于分离回收、环境友好、反应条件温和的特点。
The invention discloses a method for catalytic oxidation of saturated hydrocarbon compounds, which is characterized in that chitosan amino acid derivatives (or chitosan) are used as ligands to prepare chitosan-based metal complexes, and the obtained complexes are used as Catalyst, in the normal pressure or low pressure system, using air, O 2 , H 2 O 2 or CH 3 COOOH as the oxygen supply agent, the catalytic oxidation reaction of saturated hydrocarbon compounds can be used to selectively prepare oxidation products. The method involved in the invention has the characteristics of high activity, high selectivity, easy separation and recovery of catalyst, environmental friendliness and mild reaction conditions.
Description
技术领域
本发明涉及一种新型饱和烃类物质催化氧化的方法。The invention relates to a novel method for catalytic oxidation of saturated hydrocarbons.
背景技术 Background technique
饱和烃中C-H键的选择氧化一直是化学家们感兴趣的领域，也是没有解决的问题，一方面是由于这些饱和烃的C-H键的键能较高，难以氧化；另一方面是由于氧化生成的中间产物醇或醛比原料烃活泼；更容易进一步氧化成最终产物羧酸，很难高选择性地得到醇或醛。目前饱和碳原子氧化的工业生产主要是通过高价氧化剂的化学计量氧化法或高温高压下的催化氧化得到，化学氧化法存在转化率普遍较低，且存在很严重的环境污染问题；而高温高压下催化氧化虽然能适当提高转化率，但其苛刻的反应条件使反应选择性较差，无法高选择性地制备醇醛中间体，而且上述催化剂存在分离回收困难、用量较大、容易中毒等问题。因此，寻找高活性、高选择性、环境友好、催化剂易分离回收的新方法对促进氧化反应的工业化应用均存在极为重要的意义。The selective oxidation of C-H bonds in saturated hydrocarbons has always been an area of interest to chemists, and it is also an unsolved problem. On the one hand, the C-H bonds of these saturated hydrocarbons have high bond energy and are difficult to oxidize; The intermediate product alcohol or aldehyde is more active than the raw material hydrocarbon; it is easier to be further oxidized to the final product carboxylic acid, and it is difficult to obtain alcohol or aldehyde with high selectivity. At present, the industrial production of saturated carbon atom oxidation is mainly obtained by stoichiometric oxidation of high-valent oxidants or catalytic oxidation under high temperature and high pressure. The conversion rate of chemical oxidation is generally low, and there are serious environmental pollution problems; Although catalytic oxidation can properly increase the conversion rate, its harsh reaction conditions make the reaction selectivity poor, and it is impossible to prepare aldol intermediates with high selectivity. Moreover, the above-mentioned catalysts have problems such as difficult separation and recovery, large dosage, and easy poisoning. Therefore, finding new methods with high activity, high selectivity, environmental friendliness, and easy separation and recovery of catalysts is of great significance to promote the industrial application of oxidation reactions.
发明内容Contents of invention
本发明的目的是提供一种饱和烃类化合物催化氧化的方法，它在于对壳聚糖进行改性制取具有氨基酸结构的壳聚糖衍生物，以所得衍生物或直接以壳聚糖为配体与多种金属离子(过渡金属、稀土金属)进行络合，制取具有酶结构的壳聚糖基高分子金属模拟酶，以所得高分子金属模拟酶在常压或低压、较低温度下催化清洁的空气、O2、H2O2或CH3COOOH对饱和烃类物质烷烃、芳烃和饱和醇进行催化氧化反应，选择性制备醇、醛中间产物。The purpose of the present invention is to provide a method for the catalytic oxidation of saturated hydrocarbons, which is to modify chitosan to prepare chitosan derivatives with amino acid structure, and use the obtained derivatives or directly use chitosan as the compound complex with various metal ions (transition metals, rare earth metals) to prepare a chitosan-based polymer metal mimetic enzyme with an enzyme structure, and the obtained polymer metal mimetic enzyme can be used at normal pressure or low pressure and at a lower temperature Catalytically clean air, O 2 , H 2 O 2 or CH 3 COOOH catalyzes the oxidation reaction of saturated hydrocarbons such as alkanes, aromatics and saturated alcohols, and selectively prepares intermediate products of alcohols and aldehydes.
本发明是这样实现的：将乙醛酸与壳聚糖进行Schiff反应，生成壳聚糖乙醛酸亚胺，利用壳聚糖乙醛酸亚胺的羧基与氨基酸进行酰基化反应，从而获得具有氨基酸结构的壳聚糖衍生物；或者氨基酸在浓H2SO4催化下直接与壳聚糖进行酰基化反应，制备壳聚糖氨基酸衍生物；将所得壳聚糖衍生物与过渡金属离子(Cu，Ni，Co，Mn，Fe，Zn，Ti，Cr，La，Pb，Rh，Pd的+2、+3价离子)，或稀土金属离子(Y、La、Pr、Nd、Er的+3价离子)作用形成高分子金属配合物，以所得金属配合物在常压或低压、较低温度下催化清洁的空气、O2、H2O2或CH3COOOH，对饱和烃类物质烷烃、芳烃和饱和醇进行催化氧化反应，即可选择性地制备氧化产物。The present invention is realized like this: carry out Schiff reaction with glyoxylic acid and chitosan, generate chitosan glyoxylate imide, utilize the carboxyl of chitosan glyoxylate imide and amino acid to carry out acylation reaction, thereby obtain the Chitosan derivatives of amino acid structure; or amino acids are directly acylated with chitosan under the catalysis of concentrated H 2 SO 4 to prepare chitosan amino acid derivatives; the resulting chitosan derivatives are combined with transition metal ions (Cu , Ni, Co, Mn, Fe, Zn, Ti, Cr, La, Pb, Rh, Pd's +2, +3 valence ions), or rare earth metal ions (Y, La, Pr, Nd, Er's +3 valence ion) to form a polymer metal complex, and the resulting metal complex catalyzes clean air, O 2 , H 2 O 2 or CH 3 COOOH at normal pressure or low pressure and at a lower temperature. Catalytic oxidation reaction with saturated alcohol can selectively prepare oxidation products.
本发明所提供的一种饱和烃类化合物催化氧化的方法存在高活性、高选择性，催化剂易于分离回收、环境友好、反应条件温和的特点。The method for the catalytic oxidation of saturated hydrocarbon compounds provided by the invention has the characteristics of high activity and high selectivity, easy separation and recovery of the catalyst, environmental friendliness and mild reaction conditions.
附图说明Description of drawings
图1是本发明一种饱和烃类化合物催化氧化的方法的工艺流程图。Fig. 1 is a process flow diagram of a method for the catalytic oxidation of saturated hydrocarbon compounds in the present invention.
具体实施方式 Detailed ways
下面结合附图进一步对本发明进行说明The present invention will be further described below in conjunction with accompanying drawing
1、以脱乙酰度60-100％的壳聚糖为原料用蒸馏水溶胀2-24h，加入5-30％乙醛酸溶液，反应2-72h，过滤，用蒸馏水洗涤，干燥得壳聚糖乙醛酸亚胺，再以壳聚糖乙醛酸亚胺与氨基酸酯在15-80℃，在pH值为1-6的条件下酸化催化反应1-72h，得壳聚糖氨基酸衍生物；所述酸化条件是指H2SO4、HCl、醋酸、磷酸。壳聚糖氨基酸衍生物制备也可通过壳聚糖直接与氨基酸，在pH值为1-6的条件下酸化催化反应1-48h，得壳聚糖氨基酸衍生物，所述酸化条件是指H2SO4、HCl、醋酸。1. Take chitosan with a degree of deacetylation of 60-100% as raw material, swell with distilled water for 2-24 hours, add 5-30% glyoxylic acid solution, react for 2-72 hours, filter, wash with distilled water, and dry to obtain chitosan B alkydimide, and then use chitosan glyoxalimine and amino acid ester to acidify and catalyze the reaction for 1-72h under the condition of pH value of 1-6 at 15-80°C to obtain chitosan amino acid derivatives; The above acidification conditions refer to H 2 SO 4 , HCl, acetic acid, phosphoric acid. Chitosan amino acid derivatives can also be prepared by directly reacting chitosan with amino acids under the condition of pH 1-6 for 1-48 hours to obtain chitosan amino acid derivatives. The acidification conditions refer to H2 SO 4 , HCl, acetic acid.
2、以壳聚糖氨基酸衍生物或直接以壳聚糖为配体，15-50℃的温度下均相或非均相反应，与过渡金属离子或稀土金属离子配位络合2-24h，制备相应的壳聚糖基金属配合物。所述均相是指水相、醋酸相或盐酸相；所述过渡金属离子是指Cu，Ni，Co，Mn，Fe，Zn，Ti，Cr，La，Pb，Rh，Pd的+2、+3价离子；所述稀土金属离子是指Y、La、Pr、Nd、Er的+3价离子。2. Using chitosan amino acid derivatives or chitosan directly as a ligand, react in a homogeneous or heterogeneous phase at a temperature of 15-50 ° C, and coordinate and complex with transition metal ions or rare earth metal ions for 2-24 hours, The corresponding chitosan-based metal complexes were prepared. Described homogeneous phase refers to water phase, acetic acid phase or hydrochloric acid phase; Described transition metal ion refers to +2, + of Cu, Ni, Co, Mn, Fe, Zn, Ti, Cr, La, Pb, Rh, Pd Trivalent ions; the rare earth metal ions refer to +3 valent ions of Y, La, Pr, Nd, Er.
3、以所得壳聚糖基金属配合物为催化剂，在常压或压力在0.1-3Mpa之间、温度在15-200℃之间，以清洁的空气、O2、H2O2或CH3COOOH为供氧剂，对饱和烃类化合物进行催化氧化反应，反应2-72h，即可选择性地制备醇、醛中间产物；所述饱和烃类化合物是指烷烃、芳烃和饱和醇。3. Using the obtained chitosan-based metal complex as a catalyst, under normal pressure or a pressure between 0.1-3Mpa and a temperature between 15-200°C, with clean air, O 2 , H 2 O 2 or CH 3 COOOH is an oxygen supply agent, and the saturated hydrocarbon compound is catalyzed and oxidized for 2-72 hours to selectively prepare intermediate products of alcohol and aldehyde; the saturated hydrocarbon compound refers to alkanes, aromatic hydrocarbons and saturated alcohols.
实施例一：Embodiment one:
以壳聚糖为配体，常温常压下，水为溶剂，与FeSO4水溶液反应5h，得壳聚糖-Fe(II)配合物(CTS-Fe)。称量CTS-Fe 0.02g，加入装有20mL甲苯的烧瓶中，再加入10mL CH3COOOH，常压，72℃，反应13h，取有机相气相色谱检测，产物中醇醛含量95％，醛约为90％，甲苯单程转化率为20％。Chitosan was used as a ligand, and water was used as a solvent at normal temperature and pressure, and reacted with FeSO 4 aqueous solution for 5 hours to obtain chitosan-Fe(II) complex (CTS-Fe). Weigh 0.02g of CTS-Fe, put it into a flask filled with 20mL of toluene, then add 10mL of CH 3 COOOH, normal pressure, 72°C, react for 13h, take the organic phase for gas chromatography detection, the aldol content in the product is 95%, the aldehyde is about It is 90%, and the single-pass conversion rate of toluene is 20%.
实施例二：Embodiment two:
向装有50mL的THF的烧瓶中，加入10mLH2SO4为催化剂，10g L-蛋氨酸、6g壳聚糖先后加入其中，50℃搅拌下反应48h，过滤，蒸馏水洗涤至中性，干燥得壳聚糖蛋氨酸衍生物。常温常压下，水为溶剂，壳聚糖蛋氨酸衍生物与Cu(OAc)2进行络合反应，反应5h，过滤，蒸馏水洗涤未络合的金属离子，干燥得壳聚糖基金属配合物(CTS-cys-Cu)。取0.04g CTS-cys-Cu在常压，沸腾，回流搅拌下，反应24h，催化10mL甲苯氧化，得苯甲醛，选择性90％，单程收率10％。Add 10mL of H 2 SO 4 into a flask containing 50mL of THF as a catalyst, add 10g of L-methionine and 6g of chitosan successively, react for 48h under stirring at 50°C, filter, wash with distilled water until neutral, and dry to obtain chitosan Glycomethionine derivatives. Under normal temperature and pressure, water is a solvent, chitosan methionine derivatives and Cu(OAc) carry out complexation reaction , react for 5h, filter, wash uncomplexed metal ions with distilled water, and dry to obtain chitosan-based metal complexes ( CTS-cys-Cu). Take 0.04g of CTS-cys-Cu under normal pressure, boiling, reflux and stirring, react for 24h, and catalyze the oxidation of 10mL of toluene to obtain benzaldehyde, with a selectivity of 90% and a one-way yield of 10%.
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| 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 |
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2005
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| 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 |
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| CN103483469A (en) * | 2013-09-26 | 2014-01-01 | 上海大学 | Preparation method for water-soluble chitosan |
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| CN108299199B (en) * | 2018-02-07 | 2020-12-22 | 兄弟科技股份有限公司 | A kind of 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 | A kind of environment-friendly sewage treatment agent and its using method and application |
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