CN100387569C - Device and method for catalytic synthesis of acetyl tri-n-butyl citrate by fixed bed reactor - Google Patents
Device and method for catalytic synthesis of acetyl tri-n-butyl citrate by fixed bed reactor Download PDFInfo
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- CN100387569C CN100387569C CNB2006100499621A CN200610049962A CN100387569C CN 100387569 C CN100387569 C CN 100387569C CN B2006100499621 A CNB2006100499621 A CN B2006100499621A CN 200610049962 A CN200610049962 A CN 200610049962A CN 100387569 C CN100387569 C CN 100387569C
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- bed reactor
- fixed
- butyl citrate
- tri
- catalytic synthesis
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Abstract
The present invention discloses a device and a method for the catalytic synthesis of acetyl tri-n-butyl citrate by a fixed bed reactor, which comprises the following steps: step 1, a catalyst and a filling material are orderly filled into a fixed bed reactor by using a direct filling method, and are preheated by constant-temperature water, and the constant temperature is kept; step 2, acetyl tri-n-butyl citrate and acetic anhydride are preheated by a preheating section, and enter into a tube-type fixed bed for reaction in order to obtain a crude product of o-acetylcitric acid tributyl ester; step 3, the crude product is distillated in a pressure-reduced type for recovering acetic anhydride and acetic acid, and is washed by an alkaline water solution and is washed by water until the water phase is in neutrality, the water is removed by pressure-reduced distillation, and then the o-acetylcitric acid tributyl ester is obtained. The method of the present invention has the advantages of simple implementation, a few devices, and easy-control operating conditions. The used catalyst has the advantages of low price, easy attainment, good catalytic performance, long service life and easy regeneration. Gas-phase chromatographic analysis proves that the purity of the obtained o-acetylcitric acid tributyl ester is higher than 99%.
Description
Technical field
The present invention relates to a kind of device and method of fixed-bed reactor catalytic synthesis of acetyl tri-n-butyl citrate.
Background technology
ATBC is novel nontoxic additive, the softening agent that can be used for plastic working industries such as food product pack, medical utensil, toy for children, personal hygiene article, plastics such as PVC, vinyl chloride vinyl acetate copolymer there is good consistency, it is good around song that plastics after its plasticising have low temperature, when sealing by fusing to thermally-stabilised, fast light, water-fast, cold-resistant.
In the process for catalytic synthesis of the ATBC that provides on the document, all be batch production, and the catalyzer that adopts is a heterogeneous catalyst, need in the reaction process to stir, catalyst loss is serious, and having reacted rear catalyst needs Separation and Recovery, inconvenient operation.
Summary of the invention
The purpose of this invention is to provide that a kind of technology is simple, product purity is high, be beneficial to the device and method that reduces production costs, is fit to the fixed-bed reactor catalytic synthesis of acetyl tri-n-butyl citrate of suitability for industrialized production.
Fixed-bed reactor catalytic synthesis of acetyl tri-n-butyl citrate device has the head tank that is connected, feed preheater, fixed-bed reactor, thick product storage tank, feed preheater has serpentine tube, serpentine tube is provided with chuck outward, chuck top is provided with the feed preheater circulating water outlet, the chuck bottom is provided with the feed preheater circulating water intake, fixed-bed reactor have reaction tubes, the reaction tubes bottom is provided with the filler back up pad, reaction tubes is provided with chuck outward, chuck top is provided with the fixed-bed reactor circulating water outlet, the bottom is provided with the fixed-bed reactor circulating water intake, is followed successively by packing layer in reaction tubes from top to bottom, catalyst layer, packing layer.
Fixed-bed reactor catalytic synthesis of acetyl tri-n-butyl citrate method may further comprise the steps:
1) catalyzer and filler are adopted direct filling method pack in order in the fixed-bed reactor, and with the thermostat(t)ed water preheating and keep constant temperature;
2) tri-n-butyl citrate and diacetyl oxide are passed through the preheating section preheating, enter tubular fixed-bed reaction then, the mol ratio of diacetyl oxide and tri-n-butyl citrate is 0.8: 1～3.0: 1, preheating also remains under 40～90 ℃ of temperature, and the apparent velocity of mixing raw material is counted 4～60g.min with cross-sectional area in tubular fixed-bed
-1.cm
-2, obtain the thick product of ATBC;
3) diacetyl oxide and acetate are reclaimed in the underpressure distillation of above-mentioned crude product elder generation, use the solution washing of 2%～5% alkali again, be washed to water then and be neutral, moisture is removed in underpressure distillation, promptly gets ATBC.
The aqueous solution of described alkali is yellow soda ash, sodium hydroxide or sodium bicarbonate aqueous solution.
The synthetic method of the ATBC that the present invention adopts is implemented simple, and equipment is few, and operational condition is easily controlled, and used catalyzer is cheap and easy to get, and catalytic performance is good, and the life-span is longer, and regeneration easily.Adopt method of the present invention under suitable condition, can make the raw material tri-n-butyl citrate change into ATBC substantially fully, avoided the problem of tri-n-butyl citrate and ATBC separation difficulty, under simple processing condition, can obtain highly purified ATBC, the ATBC purity that obtains through gas chromatographic analysis more than 99%.
Description of drawings
Accompanying drawing is a tubular fixed-bed reactor catalytic synthesis of acetyl tri-n-butyl citrate schema;
Among the figure: head tank 1, feed preheater circulating water outlet 2, feed preheater 3, feed preheater circulating water intake 4, fixed-bed reactor circulating water outlet 5, fixed-bed reactor 6, packing layer 7, catalyst layer 8, fixed-bed reactor circulating water intake 9, filler back up pad 10, thick product storage tank 11.
Embodiment
As shown in drawings, fixed-bed reactor catalytic synthesis of acetyl tri-n-butyl citrate device has the head tank 1 that is connected, feed preheater 3, fixed-bed reactor 6, thick product storage tank 11, feed preheater has serpentine tube, serpentine tube is provided with chuck outward, chuck top is provided with feed preheater circulating water outlet 2, the chuck bottom is provided with feed preheater circulating water intake 4, fixed-bed reactor 6 have reaction tubes, the reaction tubes bottom is provided with filler back up pad 10, reaction tubes is provided with chuck outward, chuck top is provided with fixed-bed reactor circulating water outlet 5, the bottom is provided with fixed-bed reactor circulating water intake 9, is followed successively by packing layer 7 in reaction tubes from top to bottom, catalyst layer 8, packing layer 7.Described catalyst layer 8 is the macropore strong acid cation exchange resin.Packing layer 7 is the bique sheet.
The yield of ATBC and employing gas-chromatography external standard method are quantitative.Used gas chromatograph is the Agilent6890N gas chromatograph.Chromatographic column: HP-55%Phenyl Methyl Siloxane Capillary30.0m * 320 μ m * 0.25 μ m, FID detects, 280 ℃ of detector temperatures, temperature programming, 150 ℃ keep 2min, are raised to 260 ℃ with 15 ℃/min again, splitting ratio 100: 1, air flow quantity 300ml/min, H
2Flow 30ml/min, carrier gas is 99.999%N
2, flow 1ml/min, 270 ℃ of injector temperatures.
Further specify the present invention below in conjunction with embodiment.Following embodiment is just in order to illustrate the content of invention, rather than limits the present invention to illustrated embodiment.
The tube inner diameter of fixed-bed reactor 6 is φ 8mm, external diameter is φ 15mm, high 700mm, from the top to the bottom, load packing section, catalyst section, packing section in the reaction tubes successively, wherein packing section adopts the bique sheet, and two sections highly are 50mm, and catalyst section filling size range is the macropore strong acid cation exchange resin of 0.45mm～1.25mm, loading height 540mm, normal pressure is operation down.
By diacetyl oxide and tri-n-butyl citrate mol ratio is 2.0: 1, and the heating cycle water temp is 70 ℃, with 5.0g.min
-1.cm
-2Flow velocity the reaction mass of said ratio is passed through bed after by the serpentine tube preheating, obtain the thick product of tributyl acetylcitrate, yield is 99.7%, does not have the peak of tri-n-butyl citrate on the gas chromatogram, illustrates that tri-n-butyl citrate transforms fully.After the thick product suction filtration that reaction is obtained reclaims catalyzer, diacetyl oxide and acetate are reclaimed in underpressure distillation, again through deionized water wash, the washing of 2% aqueous sodium carbonate, be washed to water then and be neutral, moisture is removed in underpressure distillation, promptly gets ATBC.The purity of gas chromatographic analysis ATBC is more than 99%.
Adopting above-mentioned same fixed-bed reactor, is 1.6: 1 by diacetyl oxide and tri-n-butyl citrate mol ratio, and the heating cycle water temp is 70 ℃, with 40.0g.min
-1.cm
-2Flow velocity the reaction mass of said ratio is passed through bed after by the serpentine tube preheating, obtain the thick product of tributyl acetylcitrate, yield is 99.8%, does not have the peak of tri-n-butyl citrate on the gas chromatogram, illustrates that tri-n-butyl citrate transforms fully.After the thick product suction filtration that reaction is obtained reclaims catalyzer, diacetyl oxide and acetate are reclaimed in underpressure distillation, again through deionized water wash, the washing of 2% aqueous sodium carbonate, be washed to water then and be neutral, moisture is removed in underpressure distillation, promptly gets ATBC.The purity of gas chromatographic analysis ATBC is more than 99%.
Adopting above-mentioned same fixed-bed reactor, is 2.4: 1 by diacetyl oxide and tri-n-butyl citrate mol ratio, and the heating cycle water temp is 40 ℃, with 5.0g.min
-1.cm
-2Flow velocity the reaction mass of said ratio is passed through bed after by the serpentine tube preheating, obtain the thick product of ATBC, yield is 99.0%, does not have the peak of tri-n-butyl citrate on the gas chromatogram, illustrates that tri-n-butyl citrate transforms fully.After the thick product suction filtration that reaction is obtained reclaims catalyzer, diacetyl oxide and acetate are reclaimed in underpressure distillation, again through deionized water wash, the washing of 4% aqueous sodium carbonate, be washed to water then and be neutral, moisture is removed in underpressure distillation, promptly gets ATBC.The purity of gas chromatographic analysis ATBC is more than 99%.
Embodiment 4
Adopting above-mentioned same fixed-bed reactor, is 1.8: 1 by diacetyl oxide and tri-n-butyl citrate mol ratio, and the heating cycle water temp is 80 ℃, with 26.6g.min
-1.cm
-2Flow velocity the reaction mass of said ratio is passed through bed after by the serpentine tube preheating, obtain the thick product of tributyl acetylcitrate, yield is 99.6%, does not have the peak of tri-n-butyl citrate on the gas chromatogram, illustrates that tri-n-butyl citrate transforms fully.After the thick product suction filtration that reaction is obtained reclaims catalyzer, diacetyl oxide and acetate are reclaimed in underpressure distillation, again through deionized water wash, the washing of 2% aqueous sodium carbonate, be washed to water then and be neutral, moisture is removed in underpressure distillation, promptly gets ATBC.The purity of gas chromatographic analysis ATBC is more than 99%.
Adopting above-mentioned same fixed-bed reactor, is 1.2: 1 by diacetyl oxide and tri-n-butyl citrate mol ratio, and the heating cycle water temp is 60 ℃, with 10.0g.min
-1.cm
-2Flow velocity the reaction mass of said ratio is passed through bed after by the serpentine tube preheating, obtain the thick product of tributyl acetylcitrate, yield is 93.8%, has the peak of tri-n-butyl citrate to occur on the gas chromatogram, illustrates that tri-n-butyl citrate does not transform fully.
Claims (5)
1. fixed-bed reactor catalytic synthesis of acetyl tri-n-butyl citrate device, it is characterized in that, it has the head tank (1) that is connected, feed preheater (3), fixed-bed reactor (6), thick product storage tank (11), feed preheater has serpentine tube, serpentine tube is provided with chuck outward, chuck top is provided with feed preheater circulating water outlet (2), the chuck bottom is provided with feed preheater circulating water intake (4), fixed-bed reactor (6) have reaction tubes, the reaction tubes bottom is provided with filler back up pad (10), reaction tubes is provided with chuck outward, chuck top is provided with fixed-bed reactor circulating water outlet (5), the bottom is provided with fixed-bed reactor circulating water intake (9), is followed successively by packing layer (7) in reaction tubes from top to bottom, catalyst layer (8), packing layer (7).
2. fixed-bed reactor catalytic synthesis of acetyl tri-n-butyl citrate device according to claim 1 is characterized in that described catalyst layer (8) is the macropore strong acid cation exchange resin.
3. fixed-bed reactor catalytic synthesis of acetyl tri-n-butyl citrate device according to claim 1 is characterized in that described packing layer (7) is the bique sheet.
4. fixed-bed reactor catalytic synthesis of acetyl tri-n-butyl citrate method that use is installed according to claim 1 is characterized in that may further comprise the steps:
1) catalyzer and filler are adopted direct filling method pack in order in the fixed-bed reactor (6), and with the thermostat(t)ed water preheating and keep constant temperature;
2) tri-n-butyl citrate and diacetyl oxide are passed through the preheating section preheating, enter tubular fixed-bed reaction then, the mol ratio of diacetyl oxide and tri-n-butyl citrate is 0.8: 1～3.0: 1, preheating also remains under 40～90 ℃ of temperature, and the apparent velocity of mixing raw material is counted 4～60gmin with cross-sectional area in tubular fixed-bed
-1Cm
-2, obtain the thick product of ATBC;
3) diacetyl oxide and acetate are reclaimed in the underpressure distillation of above-mentioned crude product elder generation, use the solution washing of 2%～5% alkali again, be washed to water then and be neutral, moisture is removed in underpressure distillation, promptly gets ATBC.
5. fixed-bed reactor catalytic synthesis of acetyl tri-n-butyl citrate method according to claim 4, the aqueous solution that it is characterized in that described alkali is yellow soda ash, sodium hydroxide or sodium bicarbonate aqueous solution.
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|---|---|---|---|
| CNB2006100499621A CN100387569C (en) | 2006-03-22 | 2006-03-22 | Device and method for catalytic synthesis of acetyl tri-n-butyl citrate by fixed bed reactor |
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| CNB2006100499621A CN100387569C (en) | 2006-03-22 | 2006-03-22 | Device and method for catalytic synthesis of acetyl tri-n-butyl citrate by fixed bed reactor |
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| CN100387569C true CN100387569C (en) | 2008-05-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823006A (en) * | 2010-04-08 | 2010-09-08 | 姚光纯 | Honeycomb nest proppant and process of applying same to fixed bed reactor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101205185B (en) * | 2006-12-21 | 2011-05-11 | 江苏雷蒙化工科技有限公司 | Method for purifying acetyl citrate |
| CN101353305B (en) * | 2007-07-24 | 2011-09-14 | 中山联成化学工业有限公司 | Synthetic method of high-purity acetyl tributyl citrate (ATBC) |
| CN101891616A (en) * | 2010-06-30 | 2010-11-24 | 江苏天音化工有限公司 | Continuous acylation production process of tributyl acetocitrate |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709854A (en) * | 2005-06-24 | 2005-12-21 | 浙江大学 | Catylatic synthesizing method of acetyl tri-in-butyl citrate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709854A (en) * | 2005-06-24 | 2005-12-21 | 浙江大学 | Catylatic synthesizing method of acetyl tri-in-butyl citrate |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823006A (en) * | 2010-04-08 | 2010-09-08 | 姚光纯 | Honeycomb nest proppant and process of applying same to fixed bed reactor |
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