CN1247517C - Method of aldehyde oxidation and esterification to produce carboxylic ester with ionic liquid in existence - Google Patents
Method of aldehyde oxidation and esterification to produce carboxylic ester with ionic liquid in existence Download PDFInfo
- Publication number
- CN1247517C CN1247517C CN 200310115274 CN200310115274A CN1247517C CN 1247517 C CN1247517 C CN 1247517C CN 200310115274 CN200310115274 CN 200310115274 CN 200310115274 A CN200310115274 A CN 200310115274A CN 1247517 C CN1247517 C CN 1247517C
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- reaction
- aldehyde
- catalyzer
- 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.)
- Expired - Lifetime
Links
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 44
- 150000001299 aldehydes Chemical class 0.000 title claims abstract description 22
- 150000001733 carboxylic acid esters Chemical class 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 9
- 230000032050 esterification Effects 0.000 title description 4
- 238000005886 esterification reaction Methods 0.000 title description 4
- 230000003647 oxidation Effects 0.000 title description 4
- 238000007254 oxidation reaction Methods 0.000 title description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 238000006709 oxidative esterification reaction Methods 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 230000001737 promoting effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000011949 solid catalyst Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000002994 raw material Substances 0.000 description 17
- 238000002360 preparation method Methods 0.000 description 16
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 7
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- -1 quaternary ammonium alkyl ion Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000008098 formaldehyde solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- GRONZTPUWOOUFQ-UHFFFAOYSA-M sodium;methanol;hydroxide Chemical compound [OH-].[Na+].OC GRONZTPUWOOUFQ-UHFFFAOYSA-M 0.000 description 3
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical class CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- 229910017008 AsF 6 Inorganic materials 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical class CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 229910018286 SbF 6 Inorganic materials 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Abstract
The present invention relates to a new method for preparing a carboxylic acid ester by the reaction of aldehyde and alcohol with an oxidizing agent in the existence of ionic liquid. Aldehyde and alcohol are oxidized and esterified by the method to prepare a carboxylic acid ester in the existence of ionic liquid, and the reaction conversion rate and the selectivity are high. The ionic liquid used in the reaction is used as an inert carrier of a catalyst or a reaction promoting medium. When the catalyst is in the solid state, the even dispersion of the solid catalyst can be realized, the present invention is favorable to reaction and separation operation, and the catalyst is easily recycled and regenerated. When a reacting substance and a product are unsaturated compounds, the ionic liquid has the function of polymerization inhibitor, and simultaneously, has the inhibiting function to polymerization of the reacting substance and the product. The ionic liquid used in the reaction can be recycled, and the total cost is low. The present invention has wide industrial application prospects.
Description
Technical field
The present invention relates to a kind of ionic liquid and have aldehyde and pure novel method of producing carboxylicesters down with oxidant reaction.
Background technology
Carboxylicesters is important chemical products, and producing the newer operational path of carboxylicesters at present is aldehyde and pure single step reaction oxidative esterification generation carboxylicesters under the effect of catalyzer.This patent relates generally to a kind of novel method of carrying out this reaction in the presence of ionic liquid.
Existing multinomial patent relates to aldehyde oxidation and esterification and produces separating of reaction of carboxylicesters (especially unsaturated aldehyde oxidation and esterifications such as methacrylaldehyde and propenal produce esters of unsaturated carboxylic acids reaction) and reaction after product since the seventies in 20th century.As U.S. Pat 5969178, US6107515, European patent EP 0890569, EP0972759, Japanese Patent JP-B-57-35856, JP-B-4-72578, JP-A-57-50545, JP-A-61-243044, and Chinese patent CN1207959, CN1251086 etc.
But reaction-ure conversion-age is generally lower in the above-mentioned patent, and reactant and also polymerization easily of product when used aldehyde is unsaturated aldehyde.To these problems, existing patent does not all propose effective terms of settlement.
Summary of the invention
The novel method that the present invention proposes makes aldehyde and being reflected under the ionic liquid existence of pure oxidative esterification production carboxylicesters carry out reaction conversion ratio and selectivity height; When used aldehyde is unsaturated aldehyde, double solvent and the stopper done of ionic liquid, reactant and not polymerization of product; The ionic liquid that uses in the reaction is reusable, and total cost is low, and prospects for commercial application is wide.
The concrete embodiment of the present invention is that catalyzer is dispersed in the ionic liquid uniformly, adds oxygenant, and the reaction under suitable temperature and pH value condition of aldehyde and alcohol generates carboxylicesters.After reaction was finished, product and unreacted raw material realized and the separating of catalyzer that by the distillatory mode catalyzer is stayed in the ionic liquid and reused.Repeatedly use the deactivated catalyzer in back to reclaim from ionic liquid by centrifugation, ionic liquid can continue to recycle.
The present invention is dispersed in the ionic liquid catalyzer with the mode that stirs uniformly.
The ionic liquid that uses among the present invention can by a kind of positively charged ion and a kind of negatively charged ion or several cation and several negatively charged ion constitutes, at room temperature or any ionic compound or the mixture that under response behaviour, are in a liquid state; Positively charged ion is as quaternary ammonium alkyl ion [NR
4]
+, alkyl quaternary phosphine ion [PR
4]
+, the imidazol ion that replaces of alkyl is as [bmim]
+[emim]
+, the pyridinium ion [Rpy] that replaces of alkyl
+Deng, negatively charged ion as BF
4 -, PF
6 -, TA
-(CF
3COO-), HB
-(C
3F
7COO
-), TfO
-(CF3
SO
3 -), NfO
-(C
4F
9SO
3 -), Tf
2N
-((CF
3SO
2)
2N)
-, Beti
-((C
2F
5SO
2)
2N
-), Tf
3C
-((CF
3SO
2 -)
3C
-), SbF
6 -, AsF
6 -, CB
11H
12 -(and substituent), CH
3COO
-, NO
3 -, SO
4 -, NO
2 -Deng, ionic liquid can form homogeneous phase or nonhomogeneous system with reactant and product.As an example, the present invention uses Methylimidazole class ionic liquid [bmim] [PF
6] [C
4-mim] [PF
6] etc.
The catalyzer that the present invention uses can comprise homogeneous phase and heterogeneous catalyst, as be heterogeneous catalyst, then to no any restrictions such as its state, size and dimensions for any catalyzer of energy catalysis aldehyde and alcohol generation carboxylicesters.Preferred loading type Pd catalyzer especially contains the catalyzer of Pd, Pb or Pd, Bi.More preferably composite metallic catalyst, except that Pd, Pb, Bi, other element can comprise Fe, Co, Zn, Cr, Ba, Ag, Ge, Mn, Ni, Cu, Tl and rare earth element etc.No matter be that homogeneous phase or heterogeneous catalyzer all directly add stirring reaction in the reaction system.
The used aldehyde of the present invention can be saturated aldehydes such as acetaldehyde, propionic aldehyde, isobutyric aldehyde, also can be unsaturated aldehydes such as propenal, Methylacrylaldehyde, crotonic aldehyde, can also be aromatic series aldehydes such as phenyl aldehyde.Used alcohol can be saturated alcohol, as methyl alcohol, ethanol etc., also can be unsaturated alcohols such as vinyl carbinol.
The oxygenant that uses among the present invention can be pure oxygen, air or other gaseous state, liquid state and the solids etc. with similar oxygenizement.Preferred pure oxygen and air.If oxygenant is liquid or mix together with raw material, catalyzer, ionic liquid solid-state just directly the adding in the reaction system, if gas then feeds blistering reaction in the reaction system.
The temperature that reaction is carried out among the present invention can be 20～100 ℃ a arbitrary temp, preferred 30～80 ℃.
Analyzing liquid chromatography among the present invention carries out.
Transformation efficiency and selectivity definition are as follows:
The present invention is described as follows with embodiment:
Embodiment 1
1, Preparation of catalysts
With 0.83g PdCl
2, 3.2g 60wt% nitric acid is dissolved in the 32ml water, adds 10g CaCO
3Powder.Add 50ml 5wt%NaOH and 5wt% formaldehyde solution after stirring, 70 ℃ are stirred 30min down.Get solid 1 after filtering, washing.
With 0.16gPb (NO
3)
2, 0.46gBi (NO
3)
2Be dissolved in the 20ml water, behind the adding 1.8g 60wt% nitric acid solid 1 added.Add 30ml 5wt%NaOH and 5wt% formaldehyde solution after stirring, 70 ℃ are stirred 30min down.Get solid 2 after filtering, washing.
With 0.72gFe (NO
3)
3Be dissolved in the 40ml water, add solid 2 and stir.The formaldehyde solution that adds 20ml 5wt% then.Get solid 3 after filtering, washing.
With 0.31gLa (NO
3)
3Be dissolved in the 15ml water, add solid 3 and stir.The formaldehyde solution that adds 8ml 5wt% then.Filtration, washing, vacuum-drying get catalyst P d
5Bi
2PbFeLa/CaCO
3
2, there is the oxidative esterification reaction of aldehyde down in ionic liquid
In being housed, the 200ml three-necked flask of condensation reflux unit adds 10ml ionic liquid [bmim] [PF
6], the above-mentioned catalyzer of 2.0g, 3.5g Methylacrylaldehyde and 80g methyl alcohol are regulated pH value to 10.5 with the NaOH-MeOH solution of 0.3mol/L, speed with 5ml/min is blown into oxygen, use the magnetic stirring apparatus heated and stirred, keeping temperature of reaction is 50 ℃, and reaction 4h prepares methyl methacrylate.
Reaction result sees Table 1.
Embodiment 2
Catalyzer, reaction conditions and the ionic liquid identical with embodiment 1 just change the Methylacrylaldehyde in the raw material into propenal, the preparation methyl acrylate.The results are shown in Table 1.
Embodiment 3
Catalyzer, reaction conditions and the ionic liquid identical with embodiment 1 just change the methyl alcohol in the raw material into ethanol, the preparation Jia Jibingxisuanyizhi.The results are shown in Table 1.
Embodiment 4
Catalyzer, reaction conditions and the ionic liquid identical with embodiment 2 just change the methyl alcohol in the raw material into ethanol, the preparation ethyl propenoate.The results are shown in Table 1.
Embodiment 5
Catalyzer, raw material and the reaction conditions identical with embodiment 1 just change used ionic liquid into [C
4-mim] [PF
6], the preparation methyl methacrylate.The results are shown in Table 1.
Embodiment 6
Catalyzer, raw material and the reaction conditions identical with embodiment 2 just change used ionic liquid into [C
4-mim] [PF
6], the preparation methyl acrylate.The results are shown in Table 1.
Embodiment 7
Catalyzer, raw material and the reaction conditions identical with embodiment 3 just change used ionic liquid into [C
1-mim] [PF
6], the preparation Jia Jibingxisuanyizhi.The results are shown in Table 1.
Embodiment 8
Catalyzer, raw material and the reaction conditions identical with embodiment 4 just change used ionic liquid into [C
4-mim] [PF
6], the preparation ethyl propenoate.The results are shown in Table 1.
Embodiment 9
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 1 just change used ion liquid amount into 5ml from 10ml, the preparation methyl methacrylate.The results are shown in Table 1.
Embodiment 10
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 2 just change used ion liquid amount into 5ml from 10ml, the preparation methyl acrylate.The results are shown in Table 1.
Embodiment 11
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 3 just change used ion liquid amount into 5ml from 10ml, the preparation Jia Jibingxisuanyizhi.The results are shown in Table 1.
Embodiment 12
Catalyzer, raw material, ionic liquid and the reaction conditions identical with embodiment 4 just change used ion liquid amount into 5ml from 10ml, the preparation ethyl propenoate.The results are shown in Table 1.
Embodiment 13
Catalyzer, reaction conditions and the ionic liquid identical with embodiment 1 just change the Methylacrylaldehyde in the raw material into saturated butyraldehyde, the preparation methyl-butyrate.The results are shown in Table 1.
Embodiment 14
Catalyzer, reaction conditions and the ionic liquid identical with embodiment 13 just change the methyl alcohol in the raw material into ethanol, the preparation ethyl butyrate.The results are shown in Table 1.
Embodiment 15
The product that embodiment 1 obtains is 70 ℃ of distillations down, in remaining catalyzer of distillation and ionic liquid mixture, add 3.5g Methylacrylaldehyde and 80g methyl alcohol, NaOH-MeOH solution with 0.3mol/L is regulated pH value to 10.5, speed with 5ml/min is blown into oxygen, and 50 ℃ of water-baths are reacted 4h down and prepared methyl methacrylate.The results are shown in Table 1.
Embodiment 16
The product that embodiment 2 obtains is 70 ℃ of distillations down, in remaining catalyzer of distillation and ionic liquid mixture, add 3.5g propenal and 80g methyl alcohol, NaOH-MeOH solution with 0.3mol/L is regulated pH value to 10.5, speed with 5ml/min is blown into oxygen, and 50 ℃ of water-baths are reacted 4h down and prepared methyl acrylate.The results are shown in Table 1.
Comparative example 1
Catalyzer, raw material and the reaction conditions identical with embodiment 1 just do not add ionic liquid, and the preparation methyl methacrylate the results are shown in Table 1.
The result of gained result and embodiment 1 more as can be known, the selectivity of the transformation efficiency of aldehyde and ester obviously descend (main by product be the polymeric methyl methacrylate) when not adding ionic liquid.
Comparative example 2
Catalyzer, raw material and the reaction conditions identical with embodiment 2 just do not add ionic liquid, and the preparation methyl acrylate the results are shown in Table 1.
The result of gained result and embodiment 2 more as can be known, the selectivity of the transformation efficiency of aldehyde and ester obviously descend (main by product be the polymeric methyl acrylate) when not adding ionic liquid.
Table 1 reaction result
| Transformation efficiency/% | Selectivity (not comprising polymkeric substance)/% | |
| Embodiment 1 | 99.2 | 98.5 |
| 2 | 99.3 | 98.7 |
| 3 | 98.7 | 98.4 |
| 4 | 99.0 | 98.5 |
| 5 | 98.6 | 98.0 |
| 6 | 98.5 | 98.0 |
| 7 | 98.2 | 97.8 |
| 8 | 98.8 | 98.1 |
| 9 | 99.7 | 99.1 |
| 10 | 98.9 | 98.2 |
| 11 | 98.9 | 98.8 |
| 12 | 98.8 | 98.5 |
| 13 | 99.0 | 98.5 |
| 14 | 99.1 | 99.0 |
| 15 | 99.2 | 99.7 |
| 16 | 99.0 | 98.9 |
| Comparative example 1 | 85.4 | 78.7 |
| 2 | 85.5 | 79.8 |
Claims (2)
1. a positively charged ion is the imidazol ion that alkyl replaces, and negatively charged ion is PF
6 -Aldehyde in the presence of the ionic liquid that is in a liquid state under room temperature or the response behaviour and alcohol and the oxidant reaction oxidative esterification novel method of producing carboxylicesters, it is characterized in that used catalyzer is dispersed in the described ionic liquid, the reaction in the presence of oxygenant of aldehyde and alcohol generates carboxylicesters, and the catalyzer that is adopted is the loading type Pd catalyzer.
2. method according to claim 1, used oxygenant are pure oxygen or air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310115274 CN1247517C (en) | 2003-11-27 | 2003-11-27 | Method of aldehyde oxidation and esterification to produce carboxylic ester with ionic liquid in existence |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310115274 CN1247517C (en) | 2003-11-27 | 2003-11-27 | Method of aldehyde oxidation and esterification to produce carboxylic ester with ionic liquid in existence |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1544410A CN1544410A (en) | 2004-11-10 |
| CN1247517C true CN1247517C (en) | 2006-03-29 |
Family
ID=34337291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310115274 Expired - Lifetime CN1247517C (en) | 2003-11-27 | 2003-11-27 | Method of aldehyde oxidation and esterification to produce carboxylic ester with ionic liquid in existence |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1247517C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100843594B1 (en) | 2005-09-07 | 2008-07-03 | 주식회사 엘지화학 | Preparation of organic acids from aldehyde compounds by means of liquid phase oxidation reaction |
| CN102146032A (en) * | 2010-02-10 | 2011-08-10 | 北京腾化技术有限责任公司 | Method for preparing methyl methacrylate |
| JP2013032328A (en) * | 2010-08-26 | 2013-02-14 | Sumitomo Chemical Co Ltd | Method for producing carboxylic acid ester |
| CN104694259B (en) * | 2015-02-13 | 2017-08-22 | 中国科学院广州能源研究所 | A kind of method that solubilized easily separated ionic liquid homogeneous catalysis prepares biodiesel |
| CN109772345B (en) * | 2019-01-05 | 2022-03-04 | 山东理工大学 | Preparation of nickel catalyst for synthesizing ester by aldehyde oxidation esterification and application of nickel catalyst and ionic liquid co-catalysis system |
| CN110105207B (en) * | 2019-04-22 | 2022-03-04 | 山东理工大学 | One-step oxidation esterification process and application of p-hydroxybenzaldehyde |
| CN110272344B (en) * | 2019-07-15 | 2021-08-10 | 南京林业大学 | Camphorylimidazole type ionic liquid and preparation method and application thereof |
| CN110898831B (en) * | 2019-11-27 | 2022-08-05 | 中国科学院青岛生物能源与过程研究所 | Nano-gold micelle catalyst, and preparation method and application thereof |
-
2003
- 2003-11-27 CN CN 200310115274 patent/CN1247517C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1544410A (en) | 2004-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1142823C (en) | Catalyst for oxidizing reaction | |
| CN1210513A (en) | Method of preparing aldehydes by hydroformylation with rhodium catalyst and recovery of the rhodium catalyst by extraction | |
| CN1247517C (en) | Method of aldehyde oxidation and esterification to produce carboxylic ester with ionic liquid in existence | |
| CN1931824A (en) | Process and catalyst for preparing unsaturated carboxylate continuously from unsaturated aldehyde | |
| CN1086803A (en) | Produce the circulation means of hexanodioic acid and other aliphatic dibasic acids | |
| CN1245433C (en) | Lissapol N(methyl) propenoic acid ester and its preparation and use | |
| CN1160292C (en) | Process for preparation of alcohol | |
| CN1095827C (en) | Esterification of (meth) acrylic acid with alkanol | |
| CN1134412A (en) | Zirconium compounds of sulfonic acids | |
| CN1485133A (en) | New pattern catalyst for preparing methyl methacrylate by one-step oxidation-esterification from methylacrolein | |
| CN1070169C (en) | Process for carbonylation of butadiene or butadiene derivative | |
| WO2003099756A1 (en) | A process for making ethylenically unsaturated acids and esters | |
| CN1095826C (en) | Esterification of (meth) acrylic acid with alkanol | |
| CN1244189A (en) | Process for the esterification of (meth) acrylic acid with an alkanol | |
| CN1305833C (en) | Method for producing a hydroxyacid esters | |
| CN1184801A (en) | Prenpn. of glyoxal mono acetal | |
| CN1289459C (en) | Process for purifying an organic acid | |
| CN1829679A (en) | Process for the carbonylation of conjugated dienes using a palladium catalyst system | |
| EP0147156A2 (en) | Process for the production of alpha, beta-ethylenically unsaturated esters | |
| CN100345634C (en) | Synthesis of ferro-niobium ellestadite aluminium molecular sieve from pyruvic acid | |
| CN107537529A (en) | A kind of composite catalyst synthesized for esterification and Bisphenol F and preparation method | |
| CN1566064A (en) | Process for preparing azelaic acid by oleic acid phase transfer catalytic oxidation | |
| CN1417186A (en) | method of preparing 1,3-alkyldiol with 3-hydroxy ester | |
| CN1795159A (en) | Process for the hydrocarboxylation of ethylenically unsaturated carboxylic acids | |
| CN100339347C (en) | Method for preparing 2,6-dimethylphenol |
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 | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060329 |
|
| CX01 | Expiry of patent term |