CN1680245A - Synthesis of 1,2-butyl ketoaldehyde - Google Patents
Synthesis of 1,2-butyl ketoaldehyde Download PDFInfo
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- CN1680245A CN1680245A CN 200510023709 CN200510023709A CN1680245A CN 1680245 A CN1680245 A CN 1680245A CN 200510023709 CN200510023709 CN 200510023709 CN 200510023709 A CN200510023709 A CN 200510023709A CN 1680245 A CN1680245 A CN 1680245A
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- butyleneglycol
- aldehyde
- butanone
- reaction
- silver
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Abstract
Synthesis of 1,2-butyl keto-aldehyde with nanometer silver zeolite membrane as catalyst by 1,2-butanediol gas-phase dehydrogenation and oxidation is carried out by taking metal net as catalyst skeleton, coating zeolite membrane on metal wire, depositing silver on surface of zeolite membrane by electrolytic process, directly catalyzing 1,2-butanediol by the zeolite silver catalyst, synthesizing 1,2- butyl keto-aldehyde by gas-phase dehydrogenation and oxidation, or modifying one or several element of Ag2O, Zn or Mn. The reacting temperature is 280-380deg.C, the mol ratio of oxygen and 1,2-butanediol is 1.2-3.2, LHSV=1.0-0.8hr-1. The single-pass percent conversion of 1,2-butanediol reaches to 90.4%, and the selectivity of 1,2- butyl keto-aldehyde reaches to 76.9%.
Description
Technical field
The present invention relates to by 1, the dehydrogenation of 2-butyleneglycol catalytic gas phase oxidation synthesizes 1, the method for 2-butanone aldehyde.
Technical background
1,2-butanone aldehyde (claiming the ethyl oxalic dialdehyde again) is to synthesize 1, and the intermediate of 2-butanone acid is applied to biochemical field simultaneously in a large number.
Traditional 1,2-butanone aldehyde manufacturing process is with 1, and the 2-butyleneglycol is a raw material, and electrolytic silver is as catalyzer, and gas phase oxidative dehydrogenation makes pyruvic aldehyde.The problem that this method exists is that temperature of reaction is had relatively high expectations, and temperature of reaction need be more than 500 ℃, simultaneously since catalyst for electrolytic silver to be easy at high temperature be to reunite, thereby can cause activity of such catalysts sharply to descend, the increase of reaction bed pressure.When temperature of reaction greater than more than 500 ℃, scission of link deep oxidation reaction easily takes place in raw material, catalyst surface is carbon distribution easily also.
Summary of the invention
The purpose of this invention is to provide that a kind of catalytic oxidative dehydrogenation carries out continuously, technology is simple, transformation efficiency and selectivity are high 1, the synthetic method of 2-butanone aldehyde.
Of the present invention 1,2-butyleneglycol catalytic dehydrogenation oxidation is synthetic 1 in the presence of argentum-based catalyzer, 2-butanone aldehyde, and 1 of gasification enters catalytic bed continuously and carries out dehydrogenation oxidation and react after 2-butyleneglycol and the oxygen mix, and reaction formula is:
The present invention is with 1, the 2-butyleneglycol is to enter the catalytic bed reaction after the gasification of 0.6-4.0 scope internal heating mixes with oxygen in mol ratio, catalytic bed is the nanometer silver zeolite film catalyst for preparing with layer laminate method and electrolytic process, under 200-550 ℃ of temperature, 1, the liquid hourly space velocity of 2-butyleneglycol is 0.5-10.0hr
-1React under the condition, can obtain 1 of high conversion, 1 of 2-butyleneglycol and highly selective, 2-butanone aldehyde.
Catalyzer of the present invention is a nanometer silver zeolite film catalyst, this Preparation of catalysts method synthesis obtain the nanometer novel material synthetic technology that develops rapidly recently and widely used electrolytic silver technology in the argentum-based catalyzer field.The wire netting that utilizes the layer laminate method to have good heat transfer capacity with ultra-thin zeolite membrane parcel, electrolysis is then grown on it nano-Ag particles, adds at last and adds component, and 100-200 ℃ of oven dry, roasting gets final product in 300-550 ℃ of air atmosphere.
Except that utilizing pure nanometer silver, still can in silver catalyst, add component, it can be the oxide compound of Ag, Zn, Mn, as: silver suboxide, zinc oxide, Manganse Dioxide etc.
Continuously with 1,2-butyleneglycol and oxygen preheat are mixed into the catalytic bed reaction during reaction.The dehydrogenation reaction temperature range is 200-550 ℃, oxygen and 1, and the mol ratio of 2-butyleneglycol is 0.6-4.0,1, the liquid hourly space velocity of 2-butyleneglycol is 0.5-10.0hr-1.
Above-mentioned reaction better condition is: oxygen and 1, and the mol ratio of 2-butyleneglycol is 1.2-3.2,1, the liquid hourly space velocity of 2-butyleneglycol is 1.0-8.0hr
-1, the dehydrogenation reaction temperature is 280-380 ℃.
The catalytic gas phase oxidation dehydriding is adopted in this reaction, so 1, the 2-butyleneglycol need gasify and participate in reaction, 1, the gasification of 2-butyleneglycol can adopt heating raw to adopting the method for saturation steam to realize more than the boiling point or being lower than the raw material boiling point, then with preheating after oxygen mix enter reactor after overheated and on catalyzer, carry out dehydrogenation reaction.
In the catalyzer of the present invention the three preferably content be that the content of silver nano-grain is 1% to 20% (wt%), adding components contents is 0% to 10% (wt%), the content that is surrounded by the copper mesh of zeolite membrane is 70% to 99%.Experiment proves that also the catalyzer silver nano-grain for preparing can be evenly dispersed in the surface of zeolite membrane in this scope, catalytic effect is good.
The used catalyzer of the present invention is the nanometer silver zeolite film catalyst that adopts layer laminate-electrolytic process preparation, at first ultra-thin zeolite membrane is wrapped in the surface of wire netting, electrolysis then makes electrolytic silver form nano particle and is dispersed on the zeolite membrane, during preparation as follows:
(1) employing layer laminate method grows the zeolite of individual layer nano-scale on wire netting, with the Na of the certain mole of it immersion proportioning
2OAl
2O
3SiO
2H
2In the solution of O, under 40-80 ℃ of condition, left standstill 2-5 hour; Zeolite can be the A type, NaY type etc.
(2) adopting silver nitrate solution is electrolytic solution, and silver is anode, and the wire netting that is surrounded by zeolite membrane is a catholyte, and silver nano-grain is evenly distributed on the zeolite membrane; Wire netting can be copper mesh, silver-colored net, stainless (steel) wire.
(3) can add the oxide compound that adds component on the zeolite membrane surface.
(4) with above solid 100-200 ℃ of oven dry, roasting 1-4hr in the 300-550 ℃ of air atmosphere can obtain 1, the oxidation of 2-butanediol gas phase dehydrogenation is synthetic 1, the catalyzer of 2-butanone aldehyde.
Preparation of Catalyst of the present invention adopts layer laminate-electrolytic process, low-temperature catalyzed effect is better than traditional catalyst for electrolytic silver, in the presence of the homodisperse nanometer silver zeolite film catalyst of active ingredient silver nano-grain, and 1, the 2-butyleneglycol is by gas-phase dehydrogenation preparation 1, the method for 2-butanone aldehyde.The characteristics of this method are that catalytic dehydrogenation carries out continuously, 1, and one step of 2-butanediol gas phase dehydrogenation finishes, and temperature of reaction is lower, and technology is simple, and the transformation efficiency of catalytic dehydrogenation can reach 90.4%, and selectivity can reach 76.9%.
Embodiment
Embodiment:
1. the diameter of 80 milligrams of nanometer silver zeolite film catalysts that adopt layer laminate-electrolytic process to prepare being packed into is in the stainless steel reactor of 10mm, and the content of silver nano-grain is 14% in the catalyzer, and the content that is enclosed with the copper mesh of ultra-thin zeolite membrane is 86%.Catalyzer prepares as follows:
(1) adopts the layer laminate method on copper mesh, to grow the LTA zeolite of individual layer nano-scale, it is immersed mole consist of 80Na
2O:Al
2O
3: 9SiO
2: 5000H
2In the solution of O, under 40-80 ℃ of condition, left standstill 2-5 hour;
(2) adopting silver nitrate solution is electrolytic solution, and silver is anode, and the copper mesh that is surrounded by zeolite membrane is a catholyte, and silver nano-grain is evenly distributed on the zeolite membrane;
(3) with above solid 100 ℃ of oven dry, 400 ℃ of roasting 2hr can obtain 1, the oxidation of 2-butanediol gas phase dehydrogenation is synthetic 1, the catalyzer of 2-butanone aldehyde.
With 1, the 2-butyleneglycol is squeezed into gasifier with volume pump, with the oxygen mix after the preheating, laggardly go into catalytic bed and react 1 through overheated again, the inlet amount of 2-butyleneglycol is 4.0ml/hr, the oxygen feeding flow is 1.32l/h, 360 ℃ of temperature of reaction, 1,2-butyleneglycol transformation efficiency 90.4%, the selectivity of pyruvic aldehyde are 76.9%.
2. the diameter of 80 milligrams of nanometer silver zeolite film catalysts that adopt layer laminate-electrolytic process to prepare being packed into is in the stainless steel reactor of 10mm, and the content of silver nano-grain is 2% in the catalyzer, and the content that is enclosed with the copper mesh of ultra-thin zeolite membrane is 98%, 1,2-butyleneglycol feed process is with example 1,1, and the inlet amount of 2-butyleneglycol is 4.0ml/hr, the oxygen feeding flow is 2.0l/h, 360 ℃ of temperature of reaction, 1, the transformation efficiency of 2-butyleneglycol is 88%, 1, the selectivity of 2-butanone aldehyde is 75%.
3. the diameter of 80 milligrams of nanometer silver zeolite film catalysts that adopt layer laminate-electrolytic process to prepare being packed into is in the stainless steel reactor of 10mm, and the content of silver nano-grain is 18% in the catalyzer, and the content that is enclosed with the copper mesh of ultra-thin zeolite membrane is 82%, 1,2-butyleneglycol feed process is with example 1,1, and the inlet amount of 2-butyleneglycol is 8.0ml/hr, the oxygen feeding flow is 2.0l/h, 520 ℃ of temperature of reaction, 1, the transformation efficiency of 2-butyleneglycol is 92.4%, 1, the selectivity of 2-butanone aldehyde is 56%.
4. the diameter of 120 milligrams of nanometer silver zeolite film catalysts that adopt layer laminate-electrolytic process to prepare being packed into is in the stainless steel reactor of 10mm, the content of silver nano-grain is 14% in the catalyzer, and the content that is enclosed with the copper mesh of ultra-thin zeolite membrane is 86%, 1,2-butyleneglycol feed process is with example 1,1, the inlet amount of 2-butyleneglycol is 2.0ml/hr, and the oxygen feeding flow is 1.32l/h, 220 ℃ of temperature of reaction, 1,2-butyleneglycol transformation efficiency 58.9%, the pyruvic aldehyde selectivity is 62.7%.
5. the diameter of 80 milligrams of nanometer silver zeolite film catalysts that adopt layer laminate-electrolytic process to prepare being packed into is in the stainless steel reactor of 10mm, and the content of silver nano-grain is 14% in the catalyzer, and the content that is enclosed with the silver net of ultra-thin zeolite membrane is 86%, 1,2-butyleneglycol feed process is with example 1,1, and the inlet amount of 2-butyleneglycol is 4.0ml/hr, the oxygen feeding flow is 2.0l/h, 360 ℃ of temperature of reaction, 1, the transformation efficiency of 2-butyleneglycol is 87%, 1, the selectivity of 2-butanone aldehyde is 69%.
6. the diameter of 80 milligrams of nanometer silver zeolite film catalysts that adopt layer laminate-electrolytic process to prepare being packed into is in the stainless steel reactor of 10mm, and the content of silver nano-grain is 14% in the catalyzer, and the content that is enclosed with the stainless (steel) wire of ultra-thin zeolite membrane is 86%, 1,2-butyleneglycol feed process is with example 1,1, and the inlet amount of 2-butyleneglycol is 4.0ml/hr, the oxygen feeding flow is 2.0l/h, 340 ℃ of temperature of reaction, 1, the transformation efficiency of 2-butyleneglycol is 89%, 1, the selectivity of 2-butanone aldehyde is 70%.
7. the diameter of the nanometer silver zeolite film catalyst of 80 milligrams of zinc oxide modifications that the employing layer laminate-electrolytic process prepares being packed into is in the stainless steel reactor of 10mm, the content of silver nano-grain is 14% in the catalyzer, the content of zinc oxide is 6%, the content that is enclosed with the copper mesh of ultra-thin zeolite membrane is 80%, 1,2-butyleneglycol feed process is with example 1,1, the inlet amount of 2-butyleneglycol is 4.0ml/hr, and the oxygen feeding flow is 2.0l/h, 360 ℃ of temperature of reaction, 1, the transformation efficiency of 2-butyleneglycol is 87%, 1, and the selectivity of 2-butanone aldehyde is 68%.
8. the diameter of 80 milligrams of nanometer silver zeolite film catalysts that adopt layer laminate-electrolytic process to prepare being packed into is in the stainless steel reactor of 10mm, its mesolite is a NaY type zeolite, the content of silver nano-grain is 14% in the catalyzer, the content that is enclosed with the copper mesh of ultra-thin zeolite membrane is 86%, 1,2-butyleneglycol feed process is with example 1,1, the inlet amount of 2-butyleneglycol is 4.0ml/hr, and the oxygen feeding flow is 2.0l/h, 360 ℃ of temperature of reaction, 1, the transformation efficiency of 2-butyleneglycol is 86%, 1, and the selectivity of 2-butanone aldehyde is 69%.
Claims (6)
1. one kind 1, the synthetic method of 2-butanone aldehyde, be by 1, the 2-butyleneglycol is the gas phase catalytic oxidative dehydrogenation in the presence of the silver zeolite film catalyst, be about to 1, the gasification of 2-butyleneglycol enters reactor then with after the oxygen mix heating of preheating, carry out dehydrogenation reaction on catalyzer, its concrete reaction conditions is as follows:
(1) oxygen and 1, the mol ratio of 2-propylene glycol is 0.6-4.0;
The liquid hourly space velocity of (2) 1,2-butyleneglycols is 0.5-10.0hr
-1
(3) the dehydrogenation oxidation temperature of reaction is 200-450 ℃.
2. according to claim 11, the synthetic method of 2-butanone aldehyde is characterized in that oxygen and 1, and the mol ratio of 2-butyleneglycol is 1.2-3.2.
3. according to claim 11, the synthetic method of 2-butanone aldehyde is characterized in that 1, and the liquid hourly space velocity of 2-butyleneglycol is 1.0-8.0hr
-1
4. according to claim 11, the synthetic method of 2-butanone aldehyde is characterized in that temperature of reaction is 280-380 ℃.
5. according to claim 11, the synthetic method of 2-butanone aldehyde is characterized in that 1, the gasification of 2-butyleneglycol adopt with raw material be heated to boiling point with on realize.
6. according to claim 11, the synthetic method of 2-butanone aldehyde is characterized in that 1, and the gasification of 2-butyleneglycol is to adopt the saturation steam mode that is lower than the raw material boiling point to realize.
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|---|---|---|---|
| CN 200510023709 CN1286792C (en) | 2005-01-31 | 2005-01-31 | Synthesis of 1,2-butyl ketoaldehyde |
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|---|---|---|---|
| CN 200510023709 CN1286792C (en) | 2005-01-31 | 2005-01-31 | Synthesis of 1,2-butyl ketoaldehyde |
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|---|---|
| CN1680245A true CN1680245A (en) | 2005-10-12 |
| CN1286792C CN1286792C (en) | 2006-11-29 |
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| CN 200510023709 Expired - Fee Related CN1286792C (en) | 2005-01-31 | 2005-01-31 | Synthesis of 1,2-butyl ketoaldehyde |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116272984A (en) * | 2023-03-01 | 2023-06-23 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing gamma-butyrolactone by catalyzing 1, 4-butanediol to dehydrogenate, and preparation method and application thereof |
-
2005
- 2005-01-31 CN CN 200510023709 patent/CN1286792C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116272984A (en) * | 2023-03-01 | 2023-06-23 | 陕西延长石油（集团）有限责任公司 | Catalyst for preparing gamma-butyrolactone by catalyzing 1, 4-butanediol to dehydrogenate, and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1286792C (en) | 2006-11-29 |
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Granted publication date: 20061129 Termination date: 20100131 |