CN104096554B - A kind of catalyst of acetic acid acetone and synthetic method thereof and application - Google Patents
A kind of catalyst of acetic acid acetone and synthetic method thereof and application Download PDFInfo
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- CN104096554B CN104096554B CN201410355218.9A CN201410355218A CN104096554B CN 104096554 B CN104096554 B CN 104096554B CN 201410355218 A CN201410355218 A CN 201410355218A CN 104096554 B CN104096554 B CN 104096554B
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Abstract
The catalyst weight of acetic acid acetone consists of: carrier: a 90%-98%, active component: 2%-10%; Carrier is SiO
2with the compound of high purity calcium aluminate cement, its mass fraction is: SiO
2=30%-60%, high purity calcium aluminate cement=40%-70%; Active component is ZrO
2, La
2o
3, CeO
2middle one; It is simply controlled that the present invention has catalyst preparation process, selective good, and active high, cost is low, the advantage of reaction process condition gentleness.
Description
Technical field
The invention belongs to a kind of catalyst and synthetic method thereof and application, be specifically related to for the catalyst of acetic acid acetone and synthetic method thereof and application.
Technical background
Acetic acid is a kind of important chemical reagent, can be used for manufacturing PET, acetate fiber and in the food industry as acidity regulator.But along with the continuous expansion of acetic acid production capacity, estimate that by 2015 domestic aggregated capacity is by breakthrough 1,000 ten thousand tons/year, and as seen that acetic acid is seriously superfluous, cause the continued downturn of acetic acid industry.Given this, develop acetic acid downstream product and there is important practical significance.
Acetone is important organic synthesis raw material, can be used for synthetic epoxy resin, lucite, medicine and agricultural chemicals, is also the solvent of high-quality simultaneously, for coating, binding agent etc., has a wide range of applications in chemical industry.The preparation method of acetone comprises isopropanol method, cumene method, fermentation method, acetylene hydration process and direct oxidation of propylene method.Current acetone industrial production is in the world based on cumene method, and in domestic acetone output, the proportion accounted for of fermentation method is comparatively large, and the Present Domestic acetone degree of self-sufficiency is not enough, still needs import.
Visible, adopt production of acetic acid acetone, be conducive to the low state alleviating acetic acid industry on the one hand, the degree of self-sufficiency of domestic acetone can be improved on the other hand, therefore have great importance.In addition, prepare acetone by acetic acid, compare cumene method cost low, and not containing benzene in acetone product.
Research about acetic acid acetone is less, as the people such as Zhu Ronghai (Acetic Acid Cracking acetone, Jiangsu teachers college journal, 1961,21-23) with common charcoal for catalyst, under the high temperature of 440-480 DEG C, make Acetic Acid Cracking acetone, in product, content of acetone reaches 7.19%-59.61%, but does not provide selective and catalyst stability data.The people such as R.Martinez (Ketonizationofaceticacidontitania-functionalizedsilicamo noliths, JournalofCatalysis, 2004,222:404-409) adopt TiO
2-SiO
2as catalyst, have studied the performance of this catalyst Dichlorodiphenyl Acetate synthesis acetone reaction, achieve good result, the selective of acetone reaches 75%; But adopting He as diluent gas in this course of reaction, during large commercial Application, the circulation of a large amount of He brings larger energy consumption.The people such as KulamaniParida (Catalyticketonisationofaceticacidovermodifiedzirconia1.E ffectofalkali-metalcationsaspromoter) adopt the modification ZrO such as Li, Na, K, Cs, Mg, Ni, Cu, Ce
2as catalyst, for the reaction of acetic acid acetone, achieve the good result compared with high product selectivity, but this process employs a large amount of N
2diluent gas (N
2acetic acid steam saturated under carrying room temperature, N as calculated
2content reach 98.4%).In addition, ZrO
2as catalyst carrier, its cost is higher undoubtedly.
Summary of the invention
The object of this invention is to provide a kind of catalyst preparation process simply controlled, selective good, active high, cost is low, the catalyst of the acetone of acetic acid in order to achieve the above object of reaction process condition gentleness and synthetic method thereof and application.
Catalyst weight of the present invention consists of:
Carrier: 90%-98%, active component: 2%-10%.
Described carrier is SiO
2with the compound of high purity calcium aluminate cement, its mass fraction is: SiO
2=30%-60%, high purity calcium aluminate cement=40%-70%.
Active component is ZrO
2, La
2o
3, CeO
2middle one.
The manufacturer of high purity calcium aluminate cement as above is for breaking a seal and becoming special refractories Co., Ltd, and specifications and models are high-purity CA-75.Leading indicator is: Al
2o
3>=74%, CaO≤26%, Fe
2o
3≤ 0.5%, MgO≤0.5%, TiO
2≤ 0.5%, SiO
2≤ 0.5%, specific area>=6000cm
2/ g.
Preparation method of the present invention is as follows:
(1) according to SiO
2take two kinds of components with high purity calcium aluminate cement ratio, be pulverized and mixed through pulverizer, then carry out ball milling 6-10h, gained powder adopts extrusion or beats sheet shaping, and finally at 300 DEG C-500 DEG C, roasting 3-5h obtains complexes carrier;
(2) with the nitrate aqueous solution of active component for maceration extract, according to catalyst composition, adopt equi-volume impregnating, active component nitrate aqueous solution is impregnated on carrier, through 100-120 DEG C of dry 12-24h, after 350 DEG C-500 DEG C roasting 3-6h, obtain finished catalyst.
Above-mentioned gained catalyst can be directly used in the reaction of acetic acid acetone.Reaction is carried out on a fixed bed, and the process conditions of reaction are 280 DEG C-400 DEG C, mass space velocity 0.1-3.5h
-1, pressure is normal pressure-0.2MPa.
The method of testing of catalyst of the present invention is: evaluating catalyst carries out on 10ml continuous-flow fixed bed, and catalyst is directly warming up to reaction temperature after loading reactor, and adopt double plunger micro pump conveying acetic acid, acetic acid enters reactor reaction after preheating.Reaction starts to get gas phase and liquid product analysis after 20-24h, and product adopts two to be furnished with Wax capillary column, PorapakT post and hydrogen flame respectively, the gas-chromatography of thermal conductivity cell detector is analyzed, and obtains conversion ratio and selective.
Catalyst of the present invention employs SiO from maximum different being of the catalyst of existing acetic acid acetone
2with the carrier of the compound of high purity calcium aluminate cement.Result of study display adopts SiO
2or high purity calcium aluminate cement is separately as carrier, the catalyst of preparation is all difficult to reach the SiO with prepared by the present invention in selective, active
2with the catalyst performance that the compound of high purity calcium aluminate cement is prepared as carrier.High performance carrier materials prepared by the present invention and SiO
2content and preparation condition have important relation separately with high purity calcium aluminate cement.When both content are in the scope that the present invention specifies, fully mix two kinds of components by ball milling, make part aluminous cement enter silica duct, then through follow-up calcination process, thus obtain SiO
2with a complete vector of each component strong interaction of high purity calcium aluminate cement, so in order to reach optimum performance, the temperature and time of the mixing of both proportionings, follow-up ball milling, roasting is all most important.In addition, high purity calcium aluminate cement is the mixture of a complicated component, its other component contained also serves important promotor action to the performance of gained catalyst, these components only have can reach optimum efficiency as adding during high purity calcium aluminate cement component, and adds poor effect by follow-up.When adopting another common aluminous cement of same producer, effect is also poor.
The present invention compared with prior art has following features:
A. SiO is adopted
2with the compound of high purity calcium aluminate cement as carrier, preparation process is simple, and cost is lower, and raw material has sufficient supply, is convenient to industrial applications;
B. adopt acetic acid as raw material, without diluent gas, reduce engineering operation cost;
C. catalyst adopts cheap component as carrier, prepared by infusion process, and catalyst preparing is simple and cost is lower;
D. the reaction temperature of catalyst is relatively low, and process conditions are gentle;
E. catalyst is selective higher, and in product, acetone is selective reaches more than 98%, and later separation load is little.Acetic acid conversion ratio reaches more than 80%.
Detailed description of the invention
The present invention is further illustrated for the following examples.Scope of the present invention is not by the restriction of these embodiments, and scope of the present invention proposes in detail in the claims.
Embodiment 1
Take 3.2gSiO
2, (manufacturer is " Kaifeng and become special refractories Co., Ltd " to 6.8g high purity calcium aluminate cement, specifications and models are high-purity CA-75, following examples are this model without the high purity calcium aluminate that specified otherwise adopts), after being pulverized and mixed, ball milling 6h, sample adopts extruded moulding, and gained strip carrier is roasting 5h at 300 DEG C, and gained compound mass fraction is SiO
2=32%, cement=68%.
Take 0.37gZr (NO
3)
45H
2o, is made into the aqueous solution, adopts above-mentioned gained compound to be carrier, is prepared by equi-volume impregnating, and through 100 DEG C of dry 24h, 350 DEG C of roasting 6h, obtain catalyst and consist of ZrO
2=2.12%, carrier=97.88%.Gained catalyst loads in reactor, is directly warming up to 280 DEG C, at normal pressure, mass space velocity 0.15h
-1under condition, acetic acid conversion ratio 90.2%, acetone selective 99.0%.Keep pressure constant, improve reaction temperature to 350 DEG C, increase mass space velocity to 0.9h
-1, acetic acid conversion ratio 91.5%, acetic acid selective 98.6%.
Embodiment 2
Take 5.8gSiO
2, 4.2g cement, after being pulverized and mixed, ball milling 10h, sample adopts that to beat sheet shaping, and gained column like catalyst carrier is roasting 3h at 500 DEG C, and gained compound mass fraction is SiO
2=58%, cement=42%.
Take 1.6gLa (NO
3)
36H
2o, is made into the aqueous solution, adopts above-mentioned gained compound to be carrier, is prepared by equi-volume impregnating, and through 110 DEG C of dry 15h, 420 DEG C of roasting 5h, obtain catalyst and consist of La
2o
3=6.02%, carrier=93.98%.Gained catalyst loads in reactor, and being directly warming up to 340 DEG C, is 0.1MPa, mass space velocity 2.0h in reaction pressure
-1under condition, acetic acid conversion ratio 80.2%, acetone selective 99.1%.
Embodiment 3
Take 4.5gSiO
2, 5.5g cement, after being pulverized and mixed, ball milling 8h, sample adopts that to beat sheet shaping, and gained column like catalyst carrier is roasting 4h at 400 DEG C, and gained compound mass fraction is SiO
2=45%, cement=55%.
Take 2.5gCe (NO
3)
36H
2o, is made into the aqueous solution, adopts above-mentioned gained compound to be carrier, is prepared by equi-volume impregnating, and through 120 DEG C of dry 12h, 500 DEG C of roasting 3h, obtain catalyst and consist of CeO
2=9.91%, carrier=90.09%.Gained catalyst loads in reactor, is directly warming up to 400 DEG C, at normal pressure, mass space velocity 3.5h
-1under condition, acetic acid conversion ratio 85.2%, acetone selective 98.2%.
Embodiment 4
Take 0.95gLa (NO
3)
36H
2o, is made into the aqueous solution, and adopt the carrier of embodiment 3, prepared by equi-volume impregnating, through 120 DEG C of dry 12h, 450 DEG C of roasting 4h, obtain catalyst and consist of La
2o
3=3.57%, carrier=96.43%.Gained catalyst loads in reactor, and being directly warming up to 380 DEG C, is 0.2MPa, mass space velocity 1.5h in reaction pressure
-1under condition, acetic acid conversion ratio 82.2%, acetone selective 99.0%.
Embodiment 5
Take 5.0gSiO
2, 5.0g cement, after being pulverized and mixed, ball milling 7h, sample adopt extruded moulding, gained column like catalyst carrier is roasting 4h at 450 DEG C, and gained compound mass fraction is SiO
2=50%, cement=50%.
Take 1.5gZr (NO
3)
45H
2o, is made into the aqueous solution, adopts above-mentioned gained compound to be carrier, is prepared by equi-volume impregnating, and through 110 DEG C of dry 16h, 400 DEG C of roasting 3h, obtain catalyst and consist of ZrO
2=8.61%, carrier=91.39%.Gained catalyst loads in reactor, is directly warming up to 380 DEG C, at normal pressure, mass space velocity 3.3h
-1under condition, acetic acid conversion ratio 90.0%, acetone selective 98.9%.
Claims (3)
1. a catalyst for acetic acid acetone, is characterized in that catalyst weight consists of:
Carrier: 90%-98%, active component: 2%-10%;
Described carrier is SiO
2with the compound of high purity calcium aluminate cement, its mass fraction is: SiO
2=30%-60%, high purity calcium aluminate cement=40%-70%;
Active component is ZrO
2, La
2o
3, CeO
2middle one;
Described high purity calcium aluminate cement leading indicator is: Al
2o
3>=74%, CaO≤26%, Fe
2o
3≤ 0.5%, MgO≤0.5%, TiO
2≤ 0.5%, SiO
2≤ 0.5%, specific area>=6000cm
2/ g.
2. the synthetic method of the catalyst of a kind of acetic acid acetone as claimed in claim 1, is characterized in that comprising the steps:
(1) according to SiO
2take two kinds of components with high purity calcium aluminate cement ratio, be pulverized and mixed through pulverizer, then carry out ball milling 6-10h, gained powder adopts extrusion or beats sheet shaping, and finally at 300 DEG C-500 DEG C, roasting 3-5h obtains complexes carrier;
(2) with the nitrate aqueous solution of active component for maceration extract, according to catalyst composition, adopt equi-volume impregnating, active component nitrate aqueous solution is impregnated on carrier, through 100-120 DEG C of dry 12-24h, after 350 DEG C-500 DEG C roasting 3-6h, obtain finished catalyst.
3. the application of the catalyst of a kind of acetic acid acetone as claimed in claim 1, is characterized in that comprising the steps:
Take acetic acid as raw material, carry out the reaction of acetic acid acetone on a fixed bed, the process conditions of reaction are 280 DEG C-400 DEG C, mass space velocity 0.1-3.5h
-1, pressure is normal pressure-0.2MPa.
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|---|---|---|---|
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| CN104096554B true CN104096554B (en) | 2016-01-20 |
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