CN101100425A - Process for synthesizing acetic ester - Google Patents
Process for synthesizing acetic ester Download PDFInfo
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- CN101100425A CN101100425A CNA2007100352439A CN200710035243A CN101100425A CN 101100425 A CN101100425 A CN 101100425A CN A2007100352439 A CNA2007100352439 A CN A2007100352439A CN 200710035243 A CN200710035243 A CN 200710035243A CN 101100425 A CN101100425 A CN 101100425A
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Abstract
Synthesis of acetate ester is carried out by taking propene or n-butylene or acetate as raw materials in proportion of 0.3-3.0 mol, passing through catalyst and pre-protective agent, taking solid acid as main catalyst, synthesis reacting in upstream fixed-bed reactor at 50-170 deg. C and 0.2-4.0 MPa and space velocity 0.1-4.0h-1. The acetate conversion rate reaches to 80%, selectivity of propene and n-butylene reaches to 93% and catalyst runs for 1000 hrs, it costs low, has higher activity, less atom loss and no pollution.
Description
One, technical field
The present invention relates to a kind of method, particularly relate to a kind of method with propylene or n-butene and acetic acid synthesized isopropyl ester of acetic acid reaction or 2-butyl acetate with low-carbon alkene and acetic acid synthesizing acetic ester.
Two, background technology
Acetic ester, it is a kind of widely used carboxylic acid ester compound, for colourless transparent liquid, fruit aroma, inflammable and explosive, volatile is arranged, mainly as solvent and extraction agent, be widely used in coating, tackiness agent, medicine, polyvinyl alcohol industries such as (or vinylon).The traditional processing technology of acetic ester, promptly generate Iso Butyl Acetate, N-BUTYL ACETATE by acetic acid and Virahol, butanols esterification under the vitriolic katalysis, its main drawback is that cost height, equipment are perishable, contaminate environment, product is difficult separates, and has equimolar water byproduct to produce in the process of reaction.
Three, summary of the invention
The object of the present invention is to provide a kind of cost low, pollution-free, product is easily separated, by the method for low-carbon alkene and acetic acid synthesizing acetic ester.
The technical solution used in the present invention is as follows: a kind of method of synthesizing acetic ester; it is characterized in that: with the propylene of mol ratio 0.3～3.0 or n-butene and acetic acid is raw material; be the main body catalyzer again with the solid acid after pre-protective material by catalyzer; in upflow fixed bed reactor, carry out building-up reactions; above-mentioned reaction conditions is 50～170 ℃ of temperature of reaction; reaction pressure 0.2～4.0Mpa, acetic acid air speed 0.1～4.0h
-1
Described solid acid comprises heteropolyacid, Zeo-karb, resistant to elevated temperatures Zeo-karb, metal oxide etc., preferred resistant to elevated temperatures Zeo-karb.High-temperature cation-exchange resin is meant that Zeo-karb handled through bromination, chlorination or nitration before sulfonation, introduce electrophilic functional group to improve the heat-resistant stability of Zeo-karb, the maximum operation (service) temperature of high-temperature cation-exchange resin can reach 170 ℃.
The pre-protective material preferred cationic of described catalyzer exchange resin, molecular sieve etc.
Described upflow fixed bed reactor is to want the corrosive of anti-acetic acid, and as making with titanium material, zirconium material or titanium lined, zirconium and other alloy material, reaction mass enters from reactor bottom.
The present invention has removed virulent metal ion of main body catalyzer and alkaline matter owing to add the pre-protective material of catalyzer before the main body catalyzer; Characteristics such as having does not have the atom loss in the main reaction process, cost is low, and is pollution-free, and product is easily separated.The acetic acid transformation efficiency reaches 80% among the present invention, and propylene, n-butene selectivity reach 9-3%, catalyzer operation 1000 hours, active not obviously decline.
Four, embodiment:
The invention will be further described according to specific embodiment below:
Embodiment 1:
With acetic acid and polymerization-grade propylene is raw material, and several catalyzer are tested under the listed condition of table 1 respectively, the results are shown in Table 1.In the table 1, air speed is the air speed of acetic acid, and transformation efficiency is an acetic acid conversion, and selectivity is the selectivity of propylene.
The reactive behavior of several catalyzer of table 1 and product distribute
| Catalyzer | The S54 resin | The D72 resin | Modified resin | High-temperature resin | Phospho-wolframic acid |
| Temperature/℃ pressure/Mpa alkene/acid is than air speed/hr -1The selective % composition/% of conversion ratio % isopropyl ester % acetic acid/m% propylene/m% isopropyl ether % C6+m％ | 120 0.65 1.05 1.0 79.2 93.3 80.91 11.83 2.07 0.23 0.75 | 130 0.70 1.05 1.5 79.5 81.1 80.82 6.6 1.98 1.75 4.62 | 110 0.52 1.05 1.1 81.3 95.5 84.76 12.02 0.42 0.60 0.89 | 105 1.0 1.05 1.0 93.6 96.4 91.63 3.66 3.14 0.38 0.86 | 185 0.5 1.05 0.4 45.2 98.6 55.28 41.60 2.28 trace 0.15 |
Embodiment 2:
With the self-control high-temperature cation-exchange resin is catalyzer, is raw material with propylene, acetic acid, acetic acid synthesized isopropyl ester under the listed condition of table 2, and the reactive behavior and the selectivity of catalyzer the results are shown in Table 2.In the table 2, air speed is the air speed of acetic acid, and transformation efficiency is an acetic acid conversion, and selectivity is the selectivity of propylene.
The activity of acetic acid synthesized isopropyl ester and selectivity under table 2 reaction conditions
| The test sequence number | 1 | 2 | 3 | 4 | 5 |
| Temperature/℃ pressure/Mpa alkene/acid is than air speed/hr -1Transformation efficiency % selectivity % | 50 0.2 3.0 0.1 1.2 98.5 | 80 1.0 1.05 0.5 21.5 96.9 | 100 1.5 1.05 1.1 85.3 96.5 | 130 2.0 1.05 3.0 40.6 94.4 | 170 4.0 0.3 4.0 25.1 75.6 |
With the self-control high-temperature cation-exchange resin is catalyzer, is raw material with butene-1, acetic acid, acetic acid synthesized secondary butyl ester under the listed condition of table 3, and the reactive behavior and the selectivity of catalyzer the results are shown in Table 3.In the table 3, air speed is the air speed of acetic acid, and transformation efficiency is the transformation efficiency of butene-1, and selectivity is the selectivity of butene-1.
The activity of acetic acid synthesized secondary butyl ester and selectivity under table 3 reaction conditions
| The test sequence number | 1 | 2 | 3 | 4 | 5 |
| Temperature/℃ pressure/Mpa alkene/acid is than air speed/hr -1Transformation efficiency % selectivity % | 92 1.0 0.65 2.0 65.1 94.5 | 105 1.5 0.65 2.0 86.8 93.6 | 130 2.0 0.50 2.0 80.3 87.5 | 140 2.0 0.50 2.0 76.4 80.5 | 160 2.5 0.50 2.0 75.2 51.3 |
Embodiment 4:
With the self-control high-temperature cation-exchange resin is catalyzer, is raw material with acetic acid and refinery's mixed butene, and the mixed butene composition sees Table 4,105 ℃ of temperature of reaction, pressure 2.0MPa, acetic acid air speed 1.0h
-1, acid/alkene mol ratio 1.4: 1, reaction outlet liquid phase material is formed and is seen Table 5.Butene-1, anti-butylene, maleic all belong to n-butene in the mixed butene, all generate 2-butyl acetate with acetic acid reaction.
Table 4 mixed butene is formed
| Composition | Normal butane | Trimethylmethane | Butene-1 | Iso-butylene | Anti-butylene | Maleic | C 5 |
| m％ | 31.4 | 0.03 | 3.79 | 2.69 | 33.83 | 28.10 | 0.16 |
Table 5 reaction outlet liquid phase material is formed
| Composition | The tert-butyl ester | Sec-butyl alcohol | Butyl ether | Carbon eight hydrocarbon | Carbon nine hydrocarbon | Secondary butyl ester | Acetic acid |
| m％ | 0.65 | 0.10 | 0.13 | 1.96 | 1.22 | 70.14 | 25.8 |
Embodiment 5:
With the external diameter be 10mm, material be the stainless steel tube of 1Cr18Ni as reactor, carry out the activity stabilized sex exploration experiment of cation exchange resin catalyst, the results are shown in Table 6.By table 6 as seen, S54 resin, two kinds of cation exchange resin catalysts of modified resin activity stability under above-mentioned test conditions are all relatively poor, and the variation tendency basically identical.
The resin catalyst inactivation mainly causes owing to its poor heat stability, the use temperature of common cation exchange resin is in 100 ℃, above 100 ℃, the active ingredient sulfonic group begins to come off, under the situation that has water to exist, falling speed is further accelerated, and the heat-resistant stability of ion exchange resin is relatively poor to have restricted it in industrial application, and is general only as the catalyzer of Treatment of Industrial Water with the preparation methyl tertiary butyl ether.The preparation method of the modified resin that adopts in the table 6 is the same with high-temperature cation-exchange resin, and the functional group content of just introducing that plays stabilization has only 1/3rd of high-temperature cation-exchange resin catalyzer.
Experiment also to S54 resin, the modified resin catalyst of inactivation carried out instrumental analysis and with live catalyst agent contrast, the results are shown in Table 7.Analysis of sulfur content in the reaction product be the results are shown in Table 8.
The activity stabilized sex exploration experiment of two kinds of cation exchange resin catalysts of table 6
| Catalyzer | The S54 resin | Modified resin |
| Temperature/℃ pressure/Mpa air speed/hr -1Acetic acid isopropyl ester 8/hr in tail propylene/ml/min liquid phase | 110 0.52 1.3 30 m％ 72 | 105 0.90 1.0 50 m％ 84.8 |
| 32 40 56 72 88 96 112 | 67.6 69.1 67.1 67.6 60.1 48.3 43.1 | 92.2 82.0 80.7 65.0 47.7 - - |
The instrumental analysis of table 7 live catalyst and poiser
| The S54 resin | Modified resin | |||
| Fresh dose | Poiser | Fresh dose | Poiser | |
| The working time/hour carbon/m% sulphur/m% specific surface/m2/g pore volume/m1/g mean pore size/A | - 44.9 17.0 41.5 0.28 264 | 112 44.6 14.5 44.0 0.28 256 | - 46.1 12.4 49.3 0.28 230 | 132 47.8 11.3 60.1 0.31 204 |
Analysis of sulfur content in table 8 reaction product
| Sample number | 1 | 2 | 3 | 4 | 5 | Acetate |
| Sulphur/ppm | 1.8 | 5 | 6 | 9 | 12 | ＜1 |
From table 7, table 8 as seen, after S54, modified resin catalyst reacted through 112,132 hours respectively, active ingredient-SO
3H loses 14.7% and 8.9% respectively, the phenomenon that this explanation resin catalyst exists sulfonic group to come off really, and this is one of catalyst deactivation major reason.This inactivation is permanent inactivation, can not regenerate, and experiment illustrates that also the thermostability of modified resin is better than S54 resin.Experiment also the metal content of decaying catalyst has been carried out analyzing and with the live catalyst contrast, analytical results sees Table 9.
Metal content in table 9 catalyzer
| Metal/ppm | Fe | Ni | Cr | Cu |
| Fresh dose of modification deactivator S54 deactivator S54 | 30380 28615 236 | 5514 923 - | 6500 6923 2.7 | 14 - - |
See that from table 9 Fe, Ni, Cr content are respectively 3.04%, 0.55%, 0.65% in the S54 decaying catalyst, mainly be acetic acid under comparatively high temps due to etching reactor and the pipeline, these metal ion exchanged catalyst active center-SO
3H among the H
+, catalyst acidity is reduced, and cover catalyst surface and cause catalyzer to harden, stoped reaction mass to contact to a certain extent with the catalyzer internal surface, this is another major cause of catalyst deactivation.
From the modified resin deactivator that unloads, the catalyst surface carbon deposit mainly is that the side reaction of propylene causes, and temperature is high more, and olefin(e) acid is more more than big more then carbon deposit, and this is the 3rd reason of catalyst deactivation.
Embodiment 6:
Unload the modified resin deactivator, with the 10%HCl solution washing number time that doubles catalyst volume, promptly commutative Fe, Ni, the Cr that removes catalyst surface.Table 10 is the reactive behavioies after the modified resin decaying catalyst is regenerated for the first time, and reaction conditions is: 110 ℃ of temperature, pressure 1.1Mpa, air speed 1.0hr
-1
Reactive behavior after table 10 modified resin decaying catalyst is regenerated for the first time
| Time (hour) | 16 | 24 | 32 | 36 |
| Isopropyl ester m% | 83.8 | 89.4 | 63.2 | 23.8 |
The table 10 explanation decaying catalyst back initial activity of regenerating for the first time recovers fine, but after recovery very fast again inactivation, reason may be to be contaminated with metals once more, therefore, catalyzer is carried out second time regenerate to verify its possibility.
The modified resin catalyst of inactivation once more after regeneration for the first time, with 10%HCl regeneration, by analysis, the Fe on the catalyzer, Ni, Cr are respectively 1.27%, 0.16%, 0.22%.Table 11 is the reactive behavioies after catalyzer is regenerated for the second time, and reaction conditions is the same.
Reactive behavior after table 11 catalyzer is regenerated for the second time
| Time (hour) | 8 | 16 | 20 |
| Isopropyl ester/m% | 62.6 | 87.2 | 74.0 |
As seen from Table 11, after catalyzer is regenerated for the second time, activation recovering, the major cause that proves catalyst deactivation thus be contaminated with metals due to.
Embodiment 7:
By above-mentioned experiment, the mechanism of catalyst deactivation is analyzed, found the major cause of catalyst deactivation.Simultaneously, in order to examine or check catalyst activity stability, in prepared in laboratory high-temperature cation-exchange resin catalyzer and carried out the catalyst activity stability experiment.Adopt titanium material fixed-bed reactor, before Primary Catalysts, add the pre-protective material of Zeo-karb, to remove to virulent metal ion of Primary Catalysts and alkaline matter; in temperature is 105 ℃; pressure is 0.95～1.15Mpa, acetic acid/propylene mol ratio 1: 1.05, and the acetic acid air speed is 1.0hr
-1Under the reaction conditions, carry out continuous acetic acid synthesized isopropyl ester test, the result shows that Iso Butyl Acetate content reaches about 90% in the liquid product, moves 1000 hours, and catalyst activity is more stable, and data see Table 12.
The test of table 12 self-control high-temperature catalyst activity stability
| Time h | Isopropyl ester m%* | Time h | Isopropyl ester m% | Time h | Isopropyl ester m% |
| 24 40 64 88 104 136 160 184 208 232 256 280 304 | 75.63 92.46 94.86 94.88 92.09 88.70 93.62 93.85 93.74 94.45 94.18 94.13 94.37 | 328 352 384 400 424 448 472 496 520 544 568 592 624 | 95.51 93.95 92.80 92.64 88.45 84.02 86.60 94.05 88.69 89.61 91.23 87.21 94.79 | 648 696 720 768 792 816 864 904 928 952 976 1008 1016 | 91.86 90.96 91.79 90.17 89.12 89.16 87.87 90.55 93.99 89.14 89.50 90.25 90.43 |
Remarks *: disregard and dissolve propylene in the liquid phase.
As can be seen from Table 12; the catalyzer operation is after 1000 hours; reactive behavior does not have big variation; Iso Butyl Acetate content is about 90% in the liquid phase; illustrate and adopt titanium material fixed-bed reactor; and before Primary Catalysts, add the pre-protective material of Zeo-karb and remove virulent metal ion of Primary Catalysts and alkaline matter, self-control high-temperature cation-exchange resin activity of such catalysts stability is relatively good.
Claims (3)
1, a kind of method of synthesizing acetic ester; it is characterized in that: with the propylene of mol ratio 0.3～3.0 or n-butene and acetic acid is raw material; be the main body catalyzer again with the solid acid after pre-protective material by catalyzer; in upflow fixed bed reactor, carry out building-up reactions; above-mentioned reaction conditions is 50～170 ℃ of temperature of reaction; reaction pressure 0.2～4.0Mpa, acetic acid air speed 0.1～4.0h
-1
2, method according to claim 1 is characterized in that: the preferred resistant to elevated temperatures Zeo-karb of described solid acid.
3, method according to claim 1 is characterized in that: the pre-protective material preferred cationic of described catalyzer exchange resin, molecular sieve.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100352439A CN101100425A (en) | 2007-06-26 | 2007-06-26 | Process for synthesizing acetic ester |
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| CNA2007100352439A CN101100425A (en) | 2007-06-26 | 2007-06-26 | Process for synthesizing acetic ester |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735047A (en) * | 2009-12-08 | 2010-06-16 | 南京大学 | Technology for continuously producing secbutyl acetate |
| CN102757341A (en) * | 2011-04-27 | 2012-10-31 | 中国石油化工集团公司 | Preparation method of ethyl acetate and/or isopropyl acetate |
| CN103787878A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Method for preparing sec-butyl acetate from acetic acid and n-butene |
| CN103880591A (en) * | 2012-12-24 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing isopropanol and ethanol by taking propylene and acetic acid as raw materials |
-
2007
- 2007-06-26 CN CNA2007100352439A patent/CN101100425A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735047A (en) * | 2009-12-08 | 2010-06-16 | 南京大学 | Technology for continuously producing secbutyl acetate |
| CN101735047B (en) * | 2009-12-08 | 2013-10-09 | 南京大学 | Technology for continuously producing secbutyl acetate |
| CN102757341A (en) * | 2011-04-27 | 2012-10-31 | 中国石油化工集团公司 | Preparation method of ethyl acetate and/or isopropyl acetate |
| CN103787878A (en) * | 2012-11-01 | 2014-05-14 | 中国石油化工股份有限公司 | Method for preparing sec-butyl acetate from acetic acid and n-butene |
| CN103880591A (en) * | 2012-12-24 | 2014-06-25 | 中国科学院大连化学物理研究所 | Method for preparing isopropanol and ethanol by taking propylene and acetic acid as raw materials |
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