CN1296132C - Zirconium-base catalyst for synthesis of isobutyric acid and preparation method thereof - Google Patents
Zirconium-base catalyst for synthesis of isobutyric acid and preparation method thereof Download PDFInfo
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- CN1296132C CN1296132C CNB2004100658845A CN200410065884A CN1296132C CN 1296132 C CN1296132 C CN 1296132C CN B2004100658845 A CNB2004100658845 A CN B2004100658845A CN 200410065884 A CN200410065884 A CN 200410065884A CN 1296132 C CN1296132 C CN 1296132C
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- zirconium
- rare earth
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- isobutyric acid
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Abstract
The present invention relates to a zirconium-base catalytic agent for synthesis of isobutyric acid and belongs to the technical field for preparing a catalytic agent used for fine chemical products. The present invention is composed of oxide compounds of copper, zinc and zirconium, and one kind of rare earth elements, such as lanthanum, cerium, yttrium, etc., or a plurality of kinds of rare earth elements, such as lanthanum, cerium, yttrium, etc. The content of each component according to metal is as follows: 5 to 40% of Cu, 0 to 10% of Zn, 50 to 90% of Zr and 1 to 10% of Re. Through a precipitation reaction, a precipitate maturing step, a filtration washing step, a filter cake drying roasting step, and a pulverization and strip squeezing step, or a firing sunstance obtaining step in a tabletting shape mode, the catalytic agent is prepared. The catalytic agent is used in an oxo synthesis reaction of isobutyric acid and water. The stability is good, and the conversion rate and the selectivity are high.
Description
Technical field
The invention belongs to the fine chemical product catalyst preparation technical field, refer in particular to the catalyst that a kind of synthetic isobutyric acid is used.
Background technology
Chinese patent 02148562.3 discloses " a kind of synthetic isobutyric method ", and promptly isobutylaldehyde is through the synthetic isobutyric technology of water oxidation heterogeneous catalysis.This technology replaces oxygen or air with water, has pollution-free, safety, characteristics that selectivity is high, and the main accessory substance of this technology is an isobutanol, is easy to separate, and can be recycled, and the reaction scheme of technology is:
Analyze from principle, above-mentioned reaction is reacted through the following two-step and is finished, that is:
This is pollution-free, the isobutyric acid synthesis technique of the safety of high selectivity, employed catalyst is made up of metal Cu, Zn, Al and Zr and one or more the oxide that is selected from rare earth La, Ce and Y, the shortcoming of this catalyst is a less stable, stoichiometric number hour active just sharply decline usually.
Summary of the invention
The objective of the invention is to develop a class good stability, the isobutylaldehyde that conversion ratio and selectivity are high synthesizes isobutyric catalyst through water oxidation heterogeneous catalysis, and this catalyst is equally applicable to this class synthesis catalytic reaction of n-butyric acie/propionic acid.Specifically can implement like this: Zirconium-base catalyst for synthesis of isobutyric acid, it is characterized in that the oxide of catalyst by copper, zinc, zirconium, and one or more compositions of lanthanum, cerium, yttrium class rare earth element, each component is Cu 5-40% in the content of metal, Zr50-90%, Re 1-10%, Zn≤10%.The feature of this catalyst is to be catalyst carrier with the zirconium, thereby has improved the stability of catalyst greatly.
Catalyst preparation step proposed by the invention is as follows:
1. precipitation reaction mixes the soluble-salt solution of the copper, zinc, zirconium and the rare earth element that measure and carbonate or bicarbonate aqueous solution; ,
2. slaking the 1st goes on foot the sediment of gained;
3. the sediment that the 2nd step was obtained filters, washs, filter cake oven dry roasting;
4. the burned material that the 3rd step was obtained is pulverized extrusion or compression molding.
In the Catalyst Production process, the temperature of precipitation reaction is controlled to be 50-90 ℃, and pH value is 9-11, and the time is more changeable, generally is controlled to be 5-30 minute.
The time of sediment slaking was generally 10-500 minute, preferably 60-100 minute.
The condition of filter cake oven dry roasting is: 60-150 ℃ of oven dry down, the time was generally 5-12 hour, and then 350-450 ℃ of following roasting, the time was generally 6-12 hour;
The soluble-salt solution of the copper among the preparation method, zinc, zirconium and rare earth element refers generally to nitrate or chloride etc., the sodium salt that is often referred to it as the hydrochlorate or the bicarbonate of precipitating reagent, sylvite etc.
Catalyst by this method preparation is used for isobutyric acid through water oxidation synthetic reaction, good stability, conversion ratio and selectivity height.
The specific embodiment
Embodiment 1:
Measure 160ml 1M copper nitrate solution with graduated cylinder, 31ml 1M zinc nitrate solution, 222ml 1M zirconyl chloride solution, 10ml 1M ceric ammonium nitrate solution mixes in dropping funel.In another dropping funel, add 800ml 1M sodium carbonate liquor.Under stirring state, the solution in two dropping funels is added drop-wise to simultaneously and carries out precipitation reaction in the beaker, the relative gob speed control pH value by regulating two solution about 10,80 ℃ of reaction temperatures, 30 minutes sedimentation times.After dripping, 80 ℃ of slakings 1 hour.Filter, being washed till with deionized water does not have Na in the filtrate
+And NO
3 -Ion.120 ℃ of down oven dry, after 6 hours again 400 ℃ of following roastings 9 hours.After the cooling, be broken into 100 orders, become ф 4*4mm particle with the tablet press machine compressing tablet.The weight ratio that gets each metal is Cu: Zn: Zr: Ce=30: 6: 60: 4.
Embodiment 2:
With embodiment 1, just the amount of each solution is respectively: 1M copper nitrate solution 160ml, 1M zirconyl chloride solution 230ml, 1M lanthanum nitrate hexahydrate 20ml, the temperature of precipitation reaction is controlled to be 50 ℃, and pH value is 9, precipitate 20 minutes, sediment slaking 8 hours, filter cake be 70 ℃ of down oven dry 12 hours, 350 ℃ of roastings 12 hours.The weight ratio that gets each metal is about Cu: Zr: La=30: 62: 8.
Embodiment 3:
With embodiment 1, just the amount of each solution is respectively: 1M copper nitrate solution 106ml, and 1M zinc nitrate solution 26ml, 1M zirconyl chloride solution 258ml adds 2.1 gram Y
2O
3Powder.The temperature of precipitation reaction is controlled to be 90 ℃, and pH value is 11, sediment slaking 100 minutes, filter cake is 150 ℃ of down oven dry 5 hours, 450 ℃ of roastings 6 hours, the weight ratio of each metal is about Cu: Zn: Zr: Y=20: 5: 70: 5.
Embodiment 4:
With embodiment 1, just each solution is respectively: 1M copper chloride 40ml, and 1M zinc nitrate solution 48ml, 1M zirconyl chloride solution 278ml adds 0.8 gram Y
2O
3Powder, precipitating reagent changes saleratus into, and the temperature of precipitation reaction is controlled to be 70 ℃, and pH value is 10.5, precipitates 10 minutes, sediment slaking 3 hours, filter cake is 100 ℃ of down oven dry 8 hours, 420 ℃ of roastings 10 hours.The weight ratio that gets each metal is about Cu: Zn: Zr: Y=8: 10: 80: 2
Embodiment 5:
With embodiment 1, just each solution is respectively: 1M copper chloride 220ml, and 1M zirconyl chloride solution 191ml, 1M lanthanum nitrate hexahydrate 12.6ml adds 2.2 gram Y
2O
3Powder, precipitating reagent changes sodium acid carbonate into.The temperature of precipitation reaction is controlled to be 60 ℃, and pH value is 9.5, precipitates 30 minutes, sediment slaking 30 minutes, and filter cake is 120 ℃ of down oven dry 10 hours, 380 ℃ of roastings 10 hours.The weight ratio that gets each metal is about Cu: Zr: Y: La=40: 50: 5: 5
The evaluating catalyst method:
The catalyst preliminary treatment: get the catalyst of 30g method for preparing, the internal diameter of packing into is in the reactor of 20mm, feeds to use 5%H
2/ N
2, and kept 5 hours through temperature programming to 280 in 20 hours ℃ from room temperature.
Reaction: isobutylaldehyde (18g/ hour) and water (18g/ hour) (mol ratio of isobutylaldehyde and water is 1: 4) mix vaporization, are preheated to 250 ℃, enter reactor, and 280 ℃ of reaction temperatures, reaction pressure are normal pressure.Be divided into oil reservoir and water layer after the product condensation, weighing respectively, analysis, be 1 hour sample time.The results are shown in Table 1,2.
Table 1. reaction result (react after 2 hours, analyze be gas chromatography)
| Embodiment | Oil reservoir weight (gram) | Water layer weight (gram) | Reservoir analysis is wt% as a result | Water layer analysis result wt% | ||||||
| Isobutylaldehyde | Isobutyric acid | Isobutanol | Water | Isobutylaldehyde | Isobutyric acid | Isobutanol | Water | |||
| 1 | 15.4 | 19.1 | 61.00 | 31.21 | 5.29 | 2.51 | 7.25 | 4.45 | 0.21 | 88.08 |
| 2 | 15.9 | 18.2 | 63.71 | 27.81 | 6.13 | 2.34 | 8.58 | 4.66 | 0.29 | 86.48 |
| 4 | 16.1 | 18.9 | 85.13 | 9.79 | 3.55 | 1.53 | 6.18 | 1.45 | 0.14 | 92.23 |
| 5 | 15.8 | 18.5 | 60.69 | 31.14 | 5.68 | 2.49 | 7.36 | 4.19 | 0.22 | 88.22 |
Table 2. embodiment 3 made catalyst stabilities are investigated result's (analyze and be gas chromatography)
| Reaction time (hour) | Oil reservoir weight (gram) | Water layer weight (gram) | Reservoir analysis is wt% as a result | Water layer analysis result wt% | ||||||
| Isobutylaldehyde | Isobutyric acid | Isobutanol | Water | Isobutylaldehyde | Isobutyric acid | Isobutanol | Water | |||
| 1 | 14.9 | 19.4 | 68.09 | 25.42 | 4.35 | 2.13 | 5.96 | 4.28 | 0.31 | 89.45 |
| 48 | 15.2 | 18.8 | 67.10 | 26.19 | 4.01 | 2.71 | 5.23 | 4.15 | 0.43 | 90.19 |
| 90 | 15.8 | 19.1 | 69.73 | 24.56 | 3.99 | 1.72 | 6.34 | 3.78 | 0.29 | 89.58 |
| 240 | 14.5 | 19.9 | 68.75 | 25.15 | 3.88 | 2.22 | 6.52 | 4.42 | 0.38 | 88.68 |
Claims (8)
1. Zirconium-base catalyst for synthesis of isobutyric acid is characterized in that the oxide of catalyst by copper, zinc, zirconium, and one or more rare earth elements that are selected from lanthanum, cerium, yttrium are formed, each component is Cu 5-40% in the content of metal, Zr 50-90%, rare earth element 1-10%, 0＜Zn≤10%.
2. according to the described Preparation of catalysts method of claim 1, it is characterized in that preparation process is as follows:
(1) precipitation reaction mixes the soluble-salt solution of the copper, zinc, zirconium and the rare earth element that measure and carbonate or bicarbonate aqueous solution;
(2) sediment of (1) step of slaking gained;
(3) sediment that (2) step was obtained filters, washs, filter cake oven dry roasting;
(4) (3) step is obtained burned material and pulverize extrusion or compression molding.
3. method for preparing catalyst according to claim 2, the temperature that it is characterized in that precipitation reaction is 50-90 ℃, control pH value is 9-11.
4. method for preparing catalyst according to claim 3 is characterized in that the sedimentation time is 5-30 minute.
5. method for preparing catalyst according to claim 2 is characterized in that the sedimentary curing time is 10-500 minute.
6. method for preparing catalyst according to claim 5 is characterized in that the sedimentary curing time is 60-100 minute.
7. method for preparing catalyst according to claim 2 is characterized in that filter cake oven dry and sintering temperature are respectively 60-150 ℃ and 350-450 ℃.
8. method for preparing catalyst according to claim 6 is characterized in that the drying time of filter cake is controlled to be 5-12 hour, and roasting time is controlled to be 6-12 hour.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100658845A CN1296132C (en) | 2004-12-24 | 2004-12-24 | Zirconium-base catalyst for synthesis of isobutyric acid and preparation method thereof |
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|---|---|---|---|
| CNB2004100658845A CN1296132C (en) | 2004-12-24 | 2004-12-24 | Zirconium-base catalyst for synthesis of isobutyric acid and preparation method thereof |
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| CN1296132C true CN1296132C (en) | 2007-01-24 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112169802B (en) * | 2020-09-30 | 2022-09-13 | 合肥工业大学 | Modified copper-zinc-aluminum catalyst suitable for AWS reaction and preparation method and application thereof |
| CN113185395B (en) * | 2021-04-09 | 2022-12-23 | 润泰新材料股份有限公司 | Process for the production of isobutyric acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5579339A (en) * | 1978-12-07 | 1980-06-14 | Mitsubishi Gas Chem Co Inc | Preparation of isobutyric acid and/or its ester |
| US4292437A (en) * | 1979-06-27 | 1981-09-29 | E. I. Du Pont De Nemours And Company | Preparation of isobutyric acid and esters |
| US4350829A (en) * | 1978-07-14 | 1982-09-21 | Mitsubishi Chemical Industries, Limited | Process for preparing isobutyric acid |
| US5068366A (en) * | 1990-08-06 | 1991-11-26 | Texaco Chemical Company | Simultaneous epoxide and carboxylic acid manufacture by co-oxidation in the presence of a cobalt catalyst |
| CN1386733A (en) * | 2001-05-18 | 2002-12-25 | 中国石化集团齐鲁石油化工公司 | Process for preparing isobutanoic acid |
-
2004
- 2004-12-24 CN CNB2004100658845A patent/CN1296132C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4350829A (en) * | 1978-07-14 | 1982-09-21 | Mitsubishi Chemical Industries, Limited | Process for preparing isobutyric acid |
| JPS5579339A (en) * | 1978-12-07 | 1980-06-14 | Mitsubishi Gas Chem Co Inc | Preparation of isobutyric acid and/or its ester |
| US4292437A (en) * | 1979-06-27 | 1981-09-29 | E. I. Du Pont De Nemours And Company | Preparation of isobutyric acid and esters |
| US5068366A (en) * | 1990-08-06 | 1991-11-26 | Texaco Chemical Company | Simultaneous epoxide and carboxylic acid manufacture by co-oxidation in the presence of a cobalt catalyst |
| CN1386733A (en) * | 2001-05-18 | 2002-12-25 | 中国石化集团齐鲁石油化工公司 | Process for preparing isobutanoic acid |
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