CN1114490C - Process for preparing paraoctanol by hydrogenction of paraoctanone and its catalyst - Google Patents
Process for preparing paraoctanol by hydrogenction of paraoctanone and its catalyst Download PDFInfo
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- CN1114490C CN1114490C CN00107387A CN00107387A CN1114490C CN 1114490 C CN1114490 C CN 1114490C CN 00107387 A CN00107387 A CN 00107387A CN 00107387 A CN00107387 A CN 00107387A CN 1114490 C CN1114490 C CN 1114490C
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Abstract
The present invention relates to a method for preparing secondary octyl alcohol from n-hexyl methyl ketone by way of hydrogenization and a catalyst. In the method, secondary octyl alcohol is prepared from n-hexyl methyl ketone by using a prepared special catalyst and a specific process of liquid phase hydrogenation. The prepared special catalyst does not contain chromium and other harmful substances, and has the advantages of superior catalytic activity and selectivity and favorable stability. With the catalyst, the conversion rate of n-hexyl methyl ketone reaches 99.6%, and the selectivity of secondary octyl alcohol is 99.5%.
Description
Technical field
The present invention relates to the production technology that the secondary octanone hydrogenating of a kind of usefulness is produced the catalyzer of secondary octanol and produced secondary octanol with this catalyzer.It has mainly provided a kind of direct liquid-phase hydrogenatin process and the employed catalyzer of this process from the secondary octanol of secondary octanone production high purity.
Background technology
Secondary octanol is a kind of important industrial chemicals, it is except that can be used as antifoam agent, also can be used to the raw material of synthetic softening agent, tensio-active agent, farm chemical emulgent and synthetic perfume and solvent etc., the technology of secondary octanol synthesizing hexanoic acid of this external application concentrated nitric acid oxidation and hexyl hexanoate is applied industrial.Secondary octanol can be made by the direct cracking of Viscotrol C, also can be made by secondary octanone hydrogenating.Yet there are no the patent of preparing paraoctanol by hydrogenction of paraoctanone, the catalyzer and the process condition of the ketone compounds hydrogenation system alcohol compound of patent documentation report are as follows: 1. .CN90108584 (91.10.09) has described a kind of to be raw material with Oleum Cocois and plam oil, to carry out catalyzer and preparation process thereof that alcohols is produced in medium-pressure hydrocracking.Its catalyzer is Cu-Cr-Zn ternary oxide or composite oxides, adopt the coprecipitation method preparation, but required pressure (8MPa) and temperature (230～300 ℃) is higher.2. .WO95/19844 (95.7.27) (CN94190945) has introduced a kind of cupric hydrogenization catalyst preparation method, comprise gas mixture with hydrogen or hydrogen and rare gas element, the moulding parent of liquid phase two-stage reduction copper-containing hydrogenation reaction catalyst in solvent streams, in the continuous fixed bed reaction or continuous system, can make alcohol compound through the ketone hydrogenation with this catalyzer.3. .US Pat.4,459,419 (July10,1984) have been described a kind of preparation method who loads on the ruthenium catalyst (containing ruthenium 1～2%) on the molecular sieve and to the application of organic ketone or aldehyde compound hydrogenation, have wherein been exemplified the effect of furfuryl alcohol liquid-phase hydrogenatin system tetrahydrofurfuryl alcohol.Being about 10% (accounting for furfuryl alcohol %), temperature at solvent (methyl alcohol) thinning ratio be about 5: 1 (methyl alcohol: furfuryl alcohol, volume ratio), catalyst levels is that 45 ℃, pressure are 1850psig (being roughly equal to 12.7MPa) reaction 30 minutes down, and the yield of tetrahydrofurfuryl alcohol is 100%.Though the activity and the selectivity to the furfuryl alcohol hydrogenation reaction of this catalyzer are better, owing to use noble ruthenium, the catalyzer cost is too high, and reaction pressure is high too.4. .USPat.4,182,721 (Jan.8,1980) described a kind of molybdenum modification skeletal nickel catalyst (containing molybdenum about 3～5%) the preparation method and to the application of organic ketone or aldehyde compound hydrogenation, wherein exemplified the effect of preparing furancarbinol from liquid-phase furol hydrogenation and tetrahydrofurfuryl alcohol.At solvent (Virahol) thinning ratio (Virahol: furfural that is about 2: 1, volume ratio), to be about 5% (accounting for furfural %), temperature be that 60 ℃, pressure are 300psig (being roughly equal to 2.1MPa) reaction 6 hours down to catalyst levels, the yield of tetrahydrofurfuryl alcohol is 51.9%, and the furfuryl alcohol yield is 33%.Though the reaction conditions of this catalyzer relaxes, the selectivity of reaction product is low, and product separates and purification difficult.
Summary of the invention
Purpose of the present invention provides a kind of catalyzer of preparing paraoctanol by hydrogenction of paraoctanone and uses this catalyzer to produce the production method of secondary octanol with regard to being to avoid above-mentioned the deficiencies in the prior art part, do not contain chromium and other any objectionable impurities, have very high catalytic activity, selectivity and satisfactory stability.This catalyzer is made up of cupric oxide, zinc oxide, magnesium oxide and aluminum oxide, it mainly is that aluminum oxide is carried out saturated dipping as carrier in metal salt solution, and then make after the process roasting, the weight percent of its each component is as follows, and makes its each component sum equal 100%:
Cupric oxide (CuO): 20～50% (wt%)
Zinc oxide (ZnO): 2～10% (wt%)
Magnesium oxide (MgO): 2～10% (wt%)
Aluminum oxide (Al
2O
3): 20～80% (wt%)
The metal-salt of the metal salt solution that is adopted can be nitrate, vitriol or muriate; To the saturated pickling process that aluminum oxide adopted can be to carry out in nitrate, vitriol and muriatic mixed salt solution, also can be to carry out in nitrate, vitriol or muriatic metal salt solution respectively.Its roasting process is: maturing temperature is that 300～600 ℃, time are 2～8 hours; Optimum calcination temperature is that 400～500 ℃, time are 4～6 hours.
For the production of producing secondary octanol with secondary octanone hydrogenating then is to adopt above-mentioned catalyzer, and produces with the process of liquid-phase hydrogenatin.Above-mentioned catalyzer is placed in the fixed bed, reduce with hydrogen, more secondary octanone and hydrogen are passed through bed together, the reaction pressure of its process is 1～4MPa, and temperature of reaction is 100～250 ℃, and liquid phase air speed (LHSV) is 0.1～0.5h
-1, hydrogen/oil ratio is 2000/1 (volume).The operational condition of its hydrogen reducing process is: reduction temperature is 150～300 ℃, and the recovery time is 8～15 hours, and hydrogen flowing quantity is 10～150ml/g catalyzer min.
Description of drawings
Accompanying drawing 1 is the BJH adsorption curve of the made catalyzer of the present invention.
Accompanying drawing 2 is the pore size distribution of the made catalyzer of the present invention.
Accompanying drawing 3 is the TG～DTA curve of the made catalyzer hydrogen reduction of the present invention.
Accompanying drawing 4 is the BJH desorption curve of the made catalyzer of the present invention.
Accompanying drawing 5 is the made catalyst activity of the present invention and the selectivity changing conditions with duration of service.
Embodiment
Below in conjunction with embodiment in detail technical characterstic of the present invention is described in detail.
The Preparation of catalysts method is to adopt the feasible saturated immersion process for preparing of industry usually.All catalyst preparation process may be summarized to be following several steps:
1. the preparation of support of the catalyst;
2. the preparation of metal salt solution;
3. flood;
4. dry;
5. roasting.
Catalyzer of the present invention can be used for from the hydrogenation process of the secondary octanol of secondary octanone production high purity, and the reaction pressure of process is 1～4MPa, and temperature of reaction is 100～250 ℃.
Below by embodiment in detail the present invention is described in detail:
Embodiment 1: the concentrated nitric acid that 60.0 gram SB powder (moral home-made pseudo-boehmite) is added 50ml distilled water and 1.8 grams, mix, be extruded into the bar of diameter 3mm, drying is 10 hours in 110 ℃, support of the catalyst is made in 500 ℃ of calcinations 5 hours in retort furnace then.
Embodiment 2: 140 gram cupric nitrates, 28 gram zinc nitrates, 30 gram magnesium nitrates are dissolved in the 100ml distilled water, the carrier of getting preparation in the 80 gram examples 1 floods, back in 90 ℃ of baking ovens dry 10 hours, put into 300～500 ℃ of roastings of retort furnace 5 hours, make the catalyzer of preparing paraoctanol by hydrogenction of paraoctanone.The specific surface area of institute's controlling catalyst is 100～170m
2/ g, pore volume are 0.2～0.4cm
3/ g, mean pore size is 5～10nm; BET character is shown in Fig. 1,2,4, at H
2It is middle that reductive TG～the DTA spectrogram as shown in Figure 3.
Embodiment 3: make the catalyzer of use-case 2 preparations, and on small-sized continuous hydrogenation reaction unit, reactor inside diameter 2.5cm, long 60cm, catalyzer loading amount 121.5 grams, granules of catalyst is the cylindric extrude bar of long 2～3mm, diameter 1.5～2mm.In 150～300 ℃ of temperature ranges, after 10 hours, feed raw material and carry out hydrogenation reaction with hydrogen reducing.150 ℃ of temperature of reaction, reaction pressure 2.0MPa, liquid phase air speed (LHSV) is 0.22h
-1, hydrogen/oil ratio is 2000/1 (V/V), secondary octanone transformation efficiency 99%, and secondary octanol selectivity is 97.5%.
Embodiment 4: on the reaction unit with example 3, use catalyzer and example 3 reductive conditions with example 2, temperature of reaction is 120 ℃, and reaction pressure is 4.0MPa, and liquid phase air speed (LHSV) is 0.25h
-1, hydrogen/oil ratio is 2000/1 (V/V), and secondary octanone transformation efficiency is 99.8%, and secondary octanol selectivity is 99.8%.
Embodiment 5: on reaction unit, use catalyzer and example 3 reductive conditions with example 2 with example 3, and 120 ℃ of temperature of reaction, reaction pressure 2.0MPa, liquid phase air speed (LHSV) is 0.25h
-1, hydrogen/oil ratio is 2000/1 (V/V), secondary octanone transformation efficiency 99.6%, and secondary octanol selectivity is 99.5%.
Embodiment 6: on reaction unit, use catalyzer and example 3 reductive conditions with example 2 with example 3, and 120 ℃ of temperature of reaction, reaction pressure 2.0MPa, liquid phase air speed (LHSV) is 0.50h
-1, hydrogen/oil ratio is 2000/1 (V/V), secondary octanone transformation efficiency 99.4%, and secondary octanol selectivity is 99.3%.
Successive reaction was not found catalyst deactivation in 100 hours.Catalyst activity and selectivity are seen Fig. 5 with the variation of duration of service.
The catalyzer of preparing paraoctanol by hydrogenction of paraoctanone provided by the present invention and this catalyzer of use are produced the production method of secondary octanol, preparation technology is simple, easy to operate, its catalyzer does not contain chromium and other any objectionable impurities, has very high catalytic activity, selectivity and satisfactory stability.
Claims (7)
1. catalyzer of producing secondary octanol with secondary octanone hydrogenating, it is made up of cupric oxide, zinc oxide, magnesium oxide and aluminum oxide, it is characterized in that aluminum oxide is carried out saturated dipping as carrier in metal salt solution, and then make, and make the weight percent of its each component be through roasting:
Cupric oxide: 20～50%
Zinc oxide: 2～10%
Magnesium oxide: 2～10%
Aluminum oxide: 20～80%
Above each component sum equals 100%.
2. the secondary octanone hydrogenating of usefulness according to claim 1 is produced the catalyzer of secondary octanol, it is characterized in that the metal-salt of the metal salt solution that adopted can be nitrate, vitriol or muriate.
3. the secondary octanone hydrogenating of usefulness according to claim 1 and 2 is produced the catalyzer of secondary octanol, it is characterized in that the saturated pickling process that aluminum oxide is adopted can be to carry out in nitrate, vitriol and muriatic mixed salt solution.
4. the secondary octanone hydrogenating of usefulness according to claim 1 and 2 is produced the catalyzer of secondary octanol, it is characterized in that the saturated pickling process that aluminum oxide is adopted can carry out in nitrate, vitriol or muriatic metal salt solution respectively.
5. the secondary octanone hydrogenating of usefulness according to claim 1 and 2 is produced the catalyzer of secondary octanol, it is characterized in that said roasting process is: maturing temperature is that 300～600 ℃, time are 2～8 hours.
6. method of producing secondary octanol with secondary octanone hydrogenating, mainly be to use the described catalyzer of claim 1 to adopt the process of liquid-phase hydrogenatin to produce, it is characterized in that above-mentioned catalyzer is placed in the fixed bed, use hydrogen reducing, and then secondary octanone and hydrogen passed through bed together, the reaction pressure of its process is 1～4MPa, and temperature of reaction is 100～250 ℃, and the liquid phase air speed is 0.1～0.5h
-1, hydrogen/oil volume ratio is 2000/1.
7. the secondary octanone hydrogenating of usefulness according to claim 6 is produced the method for secondary octanol, and be characterised in that said hydrogen reducing process is: reduction temperature is 150～300 ℃, and the recovery time is 8～15 hours, and hydrogen flowing quantity is 10～150ml/g catalyzer min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN00107387A CN1114490C (en) | 2000-05-12 | 2000-05-12 | Process for preparing paraoctanol by hydrogenction of paraoctanone and its catalyst |
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| CN00107387A CN1114490C (en) | 2000-05-12 | 2000-05-12 | Process for preparing paraoctanol by hydrogenction of paraoctanone and its catalyst |
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|---|---|
| CN1279127A CN1279127A (en) | 2001-01-10 |
| CN1114490C true CN1114490C (en) | 2003-07-16 |
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| CN00107387A Expired - Fee Related CN1114490C (en) | 2000-05-12 | 2000-05-12 | Process for preparing paraoctanol by hydrogenction of paraoctanone and its catalyst |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101837286A (en) * | 2010-05-20 | 2010-09-22 | 浙江工业大学 | Hydrotalcite-like compound-based magnesium-titanium-aluminum composite oxide catalyst and application thereof |
| CN102557867A (en) * | 2010-12-24 | 2012-07-11 | 中国科学院兰州化学物理研究所 | Method for producing low-medium-carbon alcohol |
| CN105566068B (en) * | 2014-11-04 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of method for beta-diketon Hydrogenation for beta-diol |
| CN105618063B (en) * | 2014-11-04 | 2018-08-17 | 中国石油化工股份有限公司 | It is a kind of for beta-diketon Hydrogenation for beta-diol catalyst |
| FR3029913B1 (en) * | 2014-12-16 | 2018-07-06 | Arkema France | 2-OCTANONE CUTTING PROCESS |
| CN108774106B (en) * | 2018-06-13 | 2021-06-18 | 山东元利科技股份有限公司 | Method for extracting sec-octanone from crude sec-octanol and hydrogenating to prepare sec-octanol and catalyst thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054060A (en) * | 1989-12-21 | 1991-08-28 | 联合碳化化学品及塑料有限公司 | With the hydrogenation that copper-aluminium-other metal catalyst carries out |
-
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- 2000-05-12 CN CN00107387A patent/CN1114490C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054060A (en) * | 1989-12-21 | 1991-08-28 | 联合碳化化学品及塑料有限公司 | With the hydrogenation that copper-aluminium-other metal catalyst carries out |
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| CN1279127A (en) | 2001-01-10 |
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