CN108607605A - A kind of catalyst for synthesizing senecioic acid methyl esters - Google Patents
A kind of catalyst for synthesizing senecioic acid methyl esters Download PDFInfo
- Publication number
- CN108607605A CN108607605A CN201810592567.0A CN201810592567A CN108607605A CN 108607605 A CN108607605 A CN 108607605A CN 201810592567 A CN201810592567 A CN 201810592567A CN 108607605 A CN108607605 A CN 108607605A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- senecioic
- methyl esters
- synthesizing
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of catalyst for synthesizing senecioic acid methyl esters, catalyst described in it is NiW/Al CA catalyst, citric acid is added in the preparation process of catalyst, and the interaction between metal component and carrier is reduced as organic acid, the carboxyl quantity of organic acid molecule is more, it interacts between decrease active metal and carrier more apparent, compared to traditional synthetic method, the easily separated recycling of catalyst reduces environmental pollution, one-step synthesis target product side reaction reduction post-processing step simplification, and the yield of product greatly improves.
Description
Technical field
The present invention relates to a kind of catalyst for synthesizing senecioic acid methyl esters, belong to chemical catalyst area.
Background technology
Senecioic acid methyl esters is widely used in the changes such as synthesis medicine, pesticide and fragrance as important fine chemical material
In chemical product.But current production technology synthetic route is long, seriously polluted, poisonous and harmful substance remains in product, invests energy
The problems such as larger are consumed, the production and application of senecioic acid methyl esters have been seriously affected.With incrementally increasing for market demand,
It is necessary to existing production technology is furtherd investigate and improved.Catalyst especially in building-up process, for combined coefficient
There is important influence.
Invention content
The purpose of the present invention is to provide a kind of catalyst for synthesizing senecioic acid methyl esters, and the catalyst is with optimal conditions
It can be catalyzed the reaction of senecioic acid and methanol, there is higher product yield.
A kind of catalyst for synthesizing senecioic acid methyl esters, the catalyst are NiW/Al-CA catalyst.
The NiW/Al-CA method for preparing catalyst is as follows：
Step 1, according to solid-liquid mass ratio be 1:100g aluminium hydrate powders are immersed in the aqueous solution of nitric acid of pH=3 by 4 ratio,
And be transferred in autoclave, then autoclave is put into baking oven and carries out hydro-thermal process, hydro-thermal process temperature is 150 DEG C, at hydro-thermal
The reason time is 8h；
After the completion of step 2, hydro-thermal process, the suspension of aluminium hydroxide powder is filtered, by filtered aluminium hydrate powder
In 120 DEG C of dry 7h, the trilobes molding of diameter 2.0mm is made into banded extruder later, then in 100 DEG C of dryings
6h, 600 DEG C of roasting 7h, obtains Al2O3Carrier；
9.2g citric acid wiring solution-formings saturation is impregnated into 100g Al by step 32O3On carrier, dry 5h, obtains at 110 DEG C
To modified with organic acids carrier Al-CA；
Above-mentioned carrier Al-CA saturations are impregnated into 0.1molL by step 4-1Nickel nitrate and 1.0molL-1Ammonium metatungstate
In mixed solution, dry 5h, obtains catalyst n iW/Al-CA at 110 DEG C.
Advantageous effect：The present invention provides a kind of catalyst for synthesizing senecioic acid methyl esters, senecioic acid and methanol
Under the action of catalyst n iW/Al-CA senecioic acid methyl esters, the preparation process of catalyst n iW/Al-CA are obtained by esterification
Middle addition citric acid reduces the interaction between metal component and carrier as organic acid, and the carboxyl quantity of organic acid molecule is got over
It is more, it interacts between decrease active metal and carrier more apparent.The addition of organic acid promotes the reduction of Ni species in catalyst,
Increase the sulphidity of active metal, and the WS generated2The crystal grain stacking number of plies increases；Ionic liquid [MIMPS] [HSO4 -] it is acid
Property ionic liquid, catalyst will be carbon-based on carboxylic acid on oxygen protonation, then reacted with alcohol.Compared to traditional synthetic method,
The easily separated recycling of catalyst reduces environmental pollution, one-step synthesis target product side reaction reduction post-processing step simplification, product
Yield greatly improve.
Specific implementation mode
Embodiment 1
A kind of method for preparing catalyst for synthesizing senecioic acid methyl esters is as follows：
Step 1, according to solid-liquid mass ratio be 1:100g aluminium hydrate powders are immersed in the aqueous solution of nitric acid of pH=3 by 4 ratio,
And be transferred in autoclave, then autoclave is put into baking oven and carries out hydro-thermal process, hydro-thermal process temperature is 150 DEG C, at hydro-thermal
The reason time is 8h；
After the completion of step 2, hydro-thermal process, the suspension of aluminium hydroxide powder is filtered, by filtered aluminium hydrate powder
In 120 DEG C of dry 7h, the trilobes molding of diameter 2.0mm is made into banded extruder later, then in 100 DEG C of dryings
6h, 600 DEG C of roasting 7h, obtains Al2O3Carrier；
9.2g citric acid wiring solution-formings saturation is impregnated into 100g Al by step 32O3On carrier, dry 5h, obtains at 110 DEG C
To modified with organic acids carrier Al-CA；
Above-mentioned carrier Al-CA saturations are impregnated into 0.1molL by step 4-1Nickel nitrate and 1.0molL-1Ammonium metatungstate
In mixed solution, dry 5h, obtains catalyst n iW/Al-CA at 110 DEG C.
A kind of synthetic method of senecioic acid methyl esters, this approach includes the following steps：
Step 1, at ambient temperature, takes the 1,3-propane sultone of equimolar amounts to be reacted with methylimidazole, is taken out after the completion of reaction
Filter is dried in vacuo 2h after anhydrous ether washing, equimolar dense HX (X=HSO is added dropwise dropwise again4 -), it is reacted under the conditions of 100 DEG C
After 8h, obtain colourless to weak yellow liquid；
Above-mentioned yellow liquid is dried in vacuo water removal by step 2, and toluene, anhydrous ether wash repeatedly removes unreacted raw material,
100 DEG C of vacuum drying 4h obtain methyl imidazolium cation type acidic ion liquid；
Step 3 is added in the 100m1 four-hole boiling flasks equipped with condenser pipe, thermometer, blender and 50ml constant pressure funnels
52g
Senecioic acid, 48g methanol and 0.1mol ionic liquids [MIMPS] [HSO4 -], 1.0g catalysis is added under heated reflux condition
Agent NiW/Al-CA reacts 3h, and gas-chromatography tracks reaction process；
Step 4, after reaction, entire organic reaction system is clearly layered with ionic-liquid catalyst, the organic liquor branched away
Body is neutralized with saturated sodium carbonate solution, and liquid separation removes water layer, and organic ester layer saturated common salt water washing is used in combination anhydrous magnesium sulfate dry
It is dry, unreacted alcohol is distilled off, vacuum distillation obtains the liquid of water white transparency, as senecioic acid methyl esters.
Embodiment 2
Step 3 is added in the 100m1 four-hole boiling flasks equipped with condenser pipe, thermometer, blender and 50ml constant pressure funnels
48g senecioic acids, 48g methanol and 0.1mol ionic liquids [MIMPS] [HSO4 -], 1.0g catalyst is added under heated reflux condition
NiW/Al-CA reacts 3h, and gas-chromatography tracks reaction process；Remaining step is the same as embodiment 1.
Embodiment 3
Step 3 is added in the 100m1 four-hole boiling flasks equipped with condenser pipe, thermometer, blender and 50ml constant pressure funnels
44g senecioic acids, 48g methanol and 0.1mol ionic liquids [MIMPS] [HSO4 -], 1.0g catalyst is added under heated reflux condition
NiW/Al-CA reacts 3h, and gas-chromatography tracks reaction process；Remaining step is the same as embodiment 1.
Embodiment 4
Step 3 is added in the 100m1 four-hole boiling flasks equipped with condenser pipe, thermometer, blender and 50ml constant pressure funnels
40g senecioic acids, 48g methanol and 0.1mol ionic liquids [MIMPS] [HSO4 -], 1.0g catalyst is added under heated reflux condition
NiW/Al-CA reacts 3h, and gas-chromatography tracks reaction process；Remaining step is the same as embodiment 1.
Embodiment 5
Step 3 is added in the 100m1 four-hole boiling flasks equipped with condenser pipe, thermometer, blender and 50ml constant pressure funnels
36g senecioic acids, 48g methanol and 0.1mol ionic liquids [MIMPS] [HSO4 -], 1.0g catalyst is added under heated reflux condition
NiW/Al-CA reacts 3h, and gas-chromatography tracks reaction process；Remaining step is the same as embodiment 1.
Embodiment 6
Step 3 is added in the 100m1 four-hole boiling flasks equipped with condenser pipe, thermometer, blender and 50ml constant pressure funnels
52g senecioic acids, 44g methanol and 0.1mol ionic liquids [MIMPS] [HSO4 -], 1.0g catalyst is added under heated reflux condition
NiW/Al-CA reacts 3h, and gas-chromatography tracks reaction process；Remaining step is the same as embodiment 1.
Embodiment 7
Step 3 is added in the 100m1 four-hole boiling flasks equipped with condenser pipe, thermometer, blender and 50ml constant pressure funnels
52g senecioic acids, 40g methanol and 0.1mol ionic liquids [MIMPS] [HSO4 -], 1.0g catalyst is added under heated reflux condition
NiW/Al-CA reacts 3h, and gas-chromatography tracks reaction process；Remaining step is the same as embodiment 1.
Embodiment 8
Step 3 is added in the 100m1 four-hole boiling flasks equipped with condenser pipe, thermometer, blender and 50ml constant pressure funnels
52g senecioic acids, 36g methanol and 0.1mol ionic liquids [MIMPS] [HSO4 -], 1.0g catalyst is added under heated reflux condition
NiW/Al-CA reacts 3h, and gas-chromatography tracks reaction process；Remaining step is the same as embodiment 1.
Embodiment 9
Step 3 is added in the 100m1 four-hole boiling flasks equipped with condenser pipe, thermometer, blender and 50ml constant pressure funnels
52g senecioic acids, 32g methanol and 0.1mol ionic liquids [MIMPS] [HSO4 -], 1.0g catalyst is added under heated reflux condition
NiW/Al-CA reacts 3h, and gas-chromatography tracks reaction process；Remaining step is the same as embodiment 1.
Embodiment 10
Step 3 is added in the 100m1 four-hole boiling flasks equipped with condenser pipe, thermometer, blender and 50ml constant pressure funnels
52g senecioic acids, 28g methanol and 0.1mol ionic liquids [MIMPS] [HSO4 -], 1.0g catalyst is added under heated reflux condition
NiW/Al-CA reacts 3h, and gas-chromatography tracks reaction process；Remaining step is the same as embodiment 1.
Reference examples 1
It is with 1 difference of embodiment：In the synthesis step 1 of intermediate, 1,3-propane sultone is with methylimidazole molar ratio
2:1, remaining step is identical with embodiment 1.
Reference examples 2
It is with 1 difference of embodiment：In the synthesis step 1 of intermediate, 1,3-propane sultone is with methylimidazole molar ratio
1:2, remaining step is identical with embodiment 1.
Reference examples 3
It is with 1 difference of embodiment：In the synthesis step 3 of intermediate, the modified with organic acids carrier Al-CA conducts of equivalent are added
Catalyst, remaining step are identical with embodiment 1.
Reference examples 4
It is with 1 difference of embodiment：In the synthesis step 3 of intermediate, composite catalyst is not added, remaining step and implementation
Example 1 is identical.
Reference examples 5
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, solid-liquid mass ratio 1:1, remaining step and embodiment 1
It is identical.
Reference examples 6
It is with 1 difference of embodiment：In the synthesis step 1 of catalyst, solid-liquid mass ratio 4:1, remaining step and embodiment 1
It is identical.
Reference examples 7
It is with 1 difference of embodiment：In the synthesis step 3 of catalyst, replace citric acid with the benzene sulfonic acid of equivalent；Remaining step
It is identical with embodiment 1.
Reference examples 8
It is with 1 difference of embodiment：In the synthesis step 3 of catalyst, with the acetic acid substituted citric acid of equivalent；Remaining step with
Embodiment 1 is identical.
Reference examples 9
It is with 1 difference of embodiment：In the synthesis step 4 of catalyst, the molar ratio of nickel nitrate and ammonium metatungstate is 1:1,
Remaining step is identical with embodiment 1.
Reference examples 10
It is with 1 difference of embodiment：In the synthesis step 4 of catalyst, the molar ratio of nickel nitrate and ammonium metatungstate is 10:1,
Remaining step is identical with embodiment 1.
It is as shown in the table for reaction result under embodiment and reference examples different condition
The experimental results showed that catalyst has good catalytic effect to the synthetic reaction of senecioic acid and methanol, in reaction item
One timing of part, intermediate yield is higher, and catalytic performance is better, otherwise poorer；Senecioic acid, methanol quality ratio are 13：When 12,
He fixes at dispensing, and synthetic effect is best, with embodiment 1 the difference lies in that embodiment 2 to embodiment 10 changes primary raw material respectively
The dosage and proportioning of senecioic acid, methanol in spite of certain effect, but are not so good as 1 high income of embodiment；Reference examples 1 are to reference examples
2 change 1,3-propane sultone and methylimidazole molar ratio, other steps are identical, and product yield is caused to be substantially reduced, and say
The component proportion of bright ionic liquid influences the product of reaction very big；Reference examples 3 to reference examples 4 do not add composite catalyst simultaneously
Use modified with organic acids carrier Al-CA as catalyst, effect is still bad, and illustrating that the load of metal salt is must can not in catalyst
Few ingredient；Reference examples 5 change the solid-liquid mass ratio of aluminium hydrate powder and salpeter solution to reference examples 6, and effect is still bad, says
Bright acid processing is insufficient to influence catalytic effect；Reference examples 7 to the benzene sulfonic acid of reference examples 8 and acetic acid substituted citric acid carries out organic
Acid is modified, is catalyzed the variation with obvious effects of reaction, illustrates that citric acid is preferable to catalyst improvement；Reference examples 9 are to reference examples
The molar ratio of 10 nickel nitrates and ammonium metatungstate changes, and the active bits number of catalyst changes, and reaction effect obviously becomes
Difference, product yield are substantially reduced；Therefore had to the synthetic reaction of senecioic acid methyl esters using the catalyst of the present invention excellent
Catalytic effect.
Claims (2)
1. a kind of catalyst for synthesizing senecioic acid methyl esters, which is characterized in that the catalyst is catalyzed for NiW/Al-CA
Agent.
2. a kind of catalyst for synthesizing senecioic acid methyl esters according to claim 1, which is characterized in that
The NiW/Al-CA method for preparing catalyst is as follows：
Step 1, according to solid-liquid mass ratio be 1:100g aluminium hydrate powders are immersed in the aqueous solution of nitric acid of pH=3 by 4 ratio,
And be transferred in autoclave, then autoclave is put into baking oven and carries out hydro-thermal process, hydro-thermal process temperature is 150 DEG C, at hydro-thermal
The reason time is 8h；
After the completion of step 2, hydro-thermal process, the suspension of aluminium hydroxide powder is filtered, by filtered aluminium hydrate powder
In 120 DEG C of dry 7h, the trilobes molding of diameter 2.0mm is made into banded extruder later, then in 100 DEG C of dryings
6h, 600 DEG C of roasting 7h, obtains Al2O3Carrier；
9.2g citric acid wiring solution-formings saturation is impregnated into 100g Al by step 32O3On carrier, dry 5h, obtains at 110 DEG C
Modified with organic acids carrier Al-CA；
Above-mentioned carrier Al-CA saturations are impregnated into 0.1molL by step 4-1Nickel nitrate and 1.0molL-1Ammonium metatungstate it is mixed
It closes in solution, dry 5h, obtains catalyst n iW/Al-CA at 110 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810592567.0A CN108607605A (en) | 2018-06-11 | 2018-06-11 | A kind of catalyst for synthesizing senecioic acid methyl esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810592567.0A CN108607605A (en) | 2018-06-11 | 2018-06-11 | A kind of catalyst for synthesizing senecioic acid methyl esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108607605A true CN108607605A (en) | 2018-10-02 |
Family
ID=63664920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810592567.0A Pending CN108607605A (en) | 2018-06-11 | 2018-06-11 | A kind of catalyst for synthesizing senecioic acid methyl esters |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108607605A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102414162A (en) * | 2009-05-07 | 2012-04-11 | 塞拉尼斯国际公司 | Vinyl ester production from acetylene and carboxylic utilizing homogeneous catalyst |
| CN103086867A (en) * | 2011-10-27 | 2013-05-08 | 中国科学院大连化学物理研究所 | Nickel base micropore material and preparation method thereof |
| CN104892668A (en) * | 2015-05-12 | 2015-09-09 | 上海大学 | Combretastatin A-4 analogue water soluble pro-prodrug, and preparation method thereof |
| CN105561993A (en) * | 2016-02-23 | 2016-05-11 | 上海华谊（集团）公司 | Catalyst for producing ethyl alcohol and co-producing ethyl acetate through acetic acid hydrogenation and preparation method |
-
2018
- 2018-06-11 CN CN201810592567.0A patent/CN108607605A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102414162A (en) * | 2009-05-07 | 2012-04-11 | 塞拉尼斯国际公司 | Vinyl ester production from acetylene and carboxylic utilizing homogeneous catalyst |
| CN103086867A (en) * | 2011-10-27 | 2013-05-08 | 中国科学院大连化学物理研究所 | Nickel base micropore material and preparation method thereof |
| CN104892668A (en) * | 2015-05-12 | 2015-09-09 | 上海大学 | Combretastatin A-4 analogue water soluble pro-prodrug, and preparation method thereof |
| CN105561993A (en) * | 2016-02-23 | 2016-05-11 | 上海华谊（集团）公司 | Catalyst for producing ethyl alcohol and co-producing ethyl acetate through acetic acid hydrogenation and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 杨义 等: "柠檬酸对NiW/γ-Al2O3加氢脱硫催化剂性能的影响", 《石油学报（石油加工）》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104277017B (en) | 2,5-dihydroxymethyl furans prepares the method for 2,5-dimethylin furans | |
| CN101733113B (en) | Catalyst used for dehydrogenation of ethyl benzene for preparing styrene and method for preparing same | |
| Bamoharram et al. | Catalytic method for synthesis of aspirin by a green, efficient and recyclable solid acid catalyst (Preyssler's anion) at room temperature | |
| CN104557562A (en) | Method for producing N,N,N',N'- tetramethylethylenediamine by virtue of direct catalytic amination of dimethylethanolamine | |
| CN104941647B (en) | Synthesize the method and loaded catalyst used of N methyl morpholines | |
| KR20090051620A (en) | Method of manufacturing glycerol ether | |
| CN103240095A (en) | Methyl acetate hydrogenation catalyst and preparation method thereof | |
| CN108558663A (en) | A kind of synthetic method of senecioic acid methyl esters | |
| CN108607605A (en) | A kind of catalyst for synthesizing senecioic acid methyl esters | |
| CN108722481A (en) | A kind of catalyst for synthesizing senecioic acid methyl esters | |
| CN103664586B (en) | Method for preparing cyclohexyl acetate and method for preparing cyclohexanol ethanol | |
| CN110759817B (en) | Preparation method of ethylene glycol mono-tert-butyl ether | |
| CN110639511B (en) | Catalyst for carbon-carbon double bond hydrogenation of acrylate and application thereof | |
| CN106890652B (en) | A kind of one step selective oxidation of methanol prepares the catalyst of dimethoxym ethane and methyl formate | |
| CN103342641A (en) | Method for synthesizing sec-butyl acetate from butene and acetic acid | |
| CN103506126B (en) | A kind of preparation method of copper radical synthesizing methanol catalyst | |
| CN104549323B (en) | The method of synthesis DMIZ 1,2 dimethylimidazole and loaded catalyst used | |
| CN108722409A (en) | Mesoporous copper-based aluminium oxide catalyst, preparation method and application | |
| CN114425367B (en) | Catalyst system for preparing acrylic ester by carbonylation of acetylene, preparation and application thereof | |
| CN111151261B (en) | Catalyst for preparing ethanol by acetate hydrogenation and application thereof | |
| CN101768040A (en) | Method for preparing propylene from butylene and ethylene | |
| CN1418729A (en) | Catalyst for producing isobutene by cracking methyl tert-butyl ether | |
| CN104971725A (en) | Catalyst for ethyl acetate hydrogenation, preparation method and applications thereof | |
| KR102118501B1 (en) | Method for preparing acrolein from glycerol | |
| CN102675095A (en) | Process for combining glycerol triacetate through acid ion liquid catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181002 |