CN1346703A - Process for preparing sec.-octanoly by hydrogenating sec.-octanone and its catalyst containing Ni - Google Patents
Process for preparing sec.-octanoly by hydrogenating sec.-octanone and its catalyst containing Ni Download PDFInfo
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- CN1346703A CN1346703A CN 01131456 CN01131456A CN1346703A CN 1346703 A CN1346703 A CN 1346703A CN 01131456 CN01131456 CN 01131456 CN 01131456 A CN01131456 A CN 01131456A CN 1346703 A CN1346703 A CN 1346703A
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Abstract
A process for preparing sec.-octanol by hydrogenating sec.-octanone and its Ni-containing catalyst are disclosed. A fixed-bed liquid-phase hydrogenation is conducted under the conditions of 0.5-2 MPa, 100-200 deg.C, 0.1-1/h of liquid-phase volume space velocity, and (200-2000):1 for the rotio of hydrogen to oil. Its advantages are high conversion up to 99.2% for sec.-octanone and selectivity up to 96% for sec.-octanol. Said catalyst has high catalytic activity, selectivity and stability.
Description
The present invention relates to a kind of method of preparing paraoctanol by hydrogenction of paraoctanone and be used for the nickeliferous catalyzer of this method, it belongs to the technology of preparing of secondary octanol.The present invention 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.
Secondary octanol is a kind of important industrial chemicals, it is except that can be used as defoamer, 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, once patent documentation was reported the catalyzer and the technology of ketone compounds hydrogenation system alcohol compound, the situation of its retrieval is as follows: 1. CN 90108584 (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 preparation method of nickel-containing hydrogenationcatalysts, comprises the gas mixture with hydrogen or hydrogen and rare gas element, the moulding parent of liquid phase two-stage reduction nickel-containing 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 (July 10,1984) 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. US Pat.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.
Method and nickeliferous catalyzer thereof that purpose of the present invention provides a kind of preparing paraoctanol by hydrogenction of paraoctanone with regard to being to avoid above-mentioned the deficiencies in the prior art part, this catalyzer does not contain chromium and other any objectionable impurities, has very high catalytic activity, selectivity and satisfactory stability.Its major technology characteristics are exactly the special-purpose nickeliferous catalyzer of purchasing in advance, get final product in the reactor of the liquid phase fixed bed that the secondary octanone of the raw material of question response is formed by catalyzer thus again.
Its major ingredient of this catalyzer is nickel oxide, basic metal or its oxide compound, transition metal oxide and aluminum oxide, the mass ratio of its each composition is: nickel oxide is 20～50%, basic metal or alkaline earth metal oxide are 2～10%, transition metal oxide is 2～10%, and aluminum oxide is 20～80%.
In process by preparing paraoctanol by hydrogenction of paraoctanone, adopt above-mentioned nickel-containing catalyst, and adopted the process of fixed bed liquid-phase hydrogenatin, the reaction pressure that makes its process is 0.5～2MPa, and temperature of reaction is 100～200 ℃, and the liquid phase air speed is 0.1～1h
-1, hydrogen/oil ratio is 200～2000/1.
Below in conjunction with embodiment in detail technical characterstic of the present invention is described in detail: on (one) Preparation of catalysts, adopt the metal salt solution pickling process to be prepared, its main step is as follows:
1. change the preparation of agent carrier: press design requirements with γ-Al
2O
3Powder adds distilled water and concentrated nitric acid, mixes all
Even, the extruding slivering, drying is 10 hours in 110 ℃, carries out through calcination process the roasting temperature again
Degree is that 400～500 ℃, time are 4～6 hours, makes support of the catalyst;
2. adopt metal salt solution to carry out dip treating: used metal-salt can be nitrate, vitriol or
Muriate, behind the dipping, drying is 10 hours in 90 ℃;
3. carry out calcination process: be about to dried catalyzer and carry out roasting, maturing temperature be 400～500 ℃,
Time is 4～6 hours, promptly makes nickel-containing catalyst.
(2) enforcement of particular content of the present invention: 1. embodiment 1 is the preparation support of the catalyst: with 120.0 gram SB powder (the German Condea product γ-Al of company
2O
3) add the concentrated nitric acids of 100ml distilled water and 2.4 grams, mix, be extruded into the bar of diameter 1.6mm, in 110 ℃ dry 10 hours, support of the catalyst was made in 500 ℃ of calcinations 5 hours in retort furnace then.2. embodiment 2 is the preparation nickel-containing catalyst: 174 gram nickelous nitrates, 10 gram zinc nitrates, 23 gram magnesium nitrates are dissolved in the 150ml distilled water, the carrier of getting preparation in the 105 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 118m
2/ g, pore volume are 0.25cm
3/ g, mean pore size is 8.3nm.3. embodiment 3 is the catalyzer that uses embodiment 2 preparations, on small-sized continuous hydrogenation reaction unit, and reactor inside diameter 2.5cm, long 60cm, catalyzer loading amount 48.4 grams, granules of catalyst is the cylindric extrude bar of length 1～2mm, diameter 1.5～2mm.In 400～500 ℃ of temperature ranges, after 8 hours, feed raw material and carry out hydrogenation reaction with hydrogen reducing.120 ℃ of temperature of reaction, reaction pressure 2.0MPa, liquid phase air speed (LHSV) is 0.25h
-1, hydrogen/oil ratio is 500/1 (V/V), secondary octanone transformation efficiency 99.2%, and secondary octanol selectivity is 96.2%.4. embodiment 4 is on the reaction unit with embodiment 3, uses with the catalyzer of embodiment 2 and the reductive condition of embodiment 3, and temperature of reaction is 120 ℃, and reaction pressure is 2.0MPa, and liquid phase air speed (LHSV) is 0.25h
-1, hydrogen/oil ratio is 200/1 (V/V), and secondary octanone transformation efficiency is 99.1%, and secondary octanol selectivity is 96.0%.5. embodiment 5 is on the reaction unit with embodiment 3, use with the catalyzer of embodiment 2 and the reductive condition of embodiment 3, and 120 ℃ of temperature of reaction, reaction pressure 1.0MPa, liquid phase air speed (LHSV) is 0.25h
-1, hydrogen/oil ratio is 200/1 (V/V), secondary octanone transformation efficiency 98.3%, and secondary octanol selectivity is 95.9%.6. embodiment 6 is on the reaction unit with embodiment 3, use with the catalyzer of embodiment 2 and the reductive condition of embodiment 3, and 120 ℃ of temperature of reaction, reaction pressure 2.0MPa, liquid phase air speed (LHSV) is 0.50h
-1, hydrogen/oil ratio is 200/1 (V/V), secondary octanone transformation efficiency 98.2%, and secondary octanol selectivity is 96.8%.Embodiment 7 be with embodiment 3 gained hydrogenation products on the 9mmHg vacuum distillation apparatus, the excision front-end volatiles, 76-80 ℃ down the main distillate fraction yield at the secondary octanol of distillation gained place be 92%, secondary octanol purity is 99.6%.
The present invention does not contain chromium and other any objectionable impurities, has excellent catalytic activity, selectivity and satisfactory stability.Adopt catalyzer of the present invention and with fixed bed liquid-phase hydrogenatin process, the transformation efficiency of secondary octanone has reached 99.2%, the selectivity of secondary octanol is 96.0%.
Claims (5)
1. the nickel-containing catalyst of a preparing paraoctanol by hydrogenction of paraoctanone, its major ingredient is nickel oxide, basic metal or its oxide compound, transition metal oxide and aluminum oxide, the mass ratio that it is characterized in that each composition is: nickel oxide is 20～50%, basic metal or alkaline earth metal oxide are 2～10%, transition metal oxide is 2～10%, and aluminum oxide is 20～80%.
2. the method for a preparing paraoctanol by hydrogenction of paraoctanone, it is characterized in that having adopted the described catalyzer of claim 1, and adopt the process of fixed bed liquid-phase hydrogenatin, the reaction pressure of its process is 0.5～2MPa, temperature of reaction is 100～200 ℃, and the liquid phase air speed is 0.1～1h
-1, hydrogen/oil ratio is 200～2000/1.
3. the nickel-containing catalyst of preparing paraoctanol by hydrogenction of paraoctanone according to claim 1 is characterized in that described nickel oxide can be NiO, and basic metal or its oxide compound can be Na
2O, K
2O, MgO, CaO or BaO, transition metal can be CoO, FeO, MoO or ZnO, and aluminum oxide can be Al
2O
3
4. the nickel-containing catalyst of preparing paraoctanol by hydrogenction of paraoctanone according to claim 1 is characterized in that described nickel-containing catalyst can adopt the metal salt solution immersion process for preparing, promptly realizes by following steps:
1. the preparation of support of the catalyst: press design requirements with γ-Al
2O
3Powder adds distilled water and concentrated nitric acid, mixes, and the extruding slivering, in 110 ℃ dry 10 hours, carry out again through calcination process, maturing temperature is that 400～500 ℃, time are 4～6 hours, makes support of the catalyst;
2. adopt metal salt solution to carry out dip treating: used metal-salt can be nitrate, vitriol or muriate, and behind the dipping, drying is 10 hours in 90 ℃;
3. carry out calcination process: be about to dried catalyzer and carry out roasting, maturing temperature is that 400～500 ℃, time are 4～6 hours, promptly makes nickel-containing catalyst.
5. according to the nickel-containing catalyst of claim 3 or 4 described preparing paraoctanol by hydrogenction of paraoctanone, it is characterized in that catalyzer must handle through hydrogen reducing, reduction temperature is 400～500 ℃, and the recovery time is 8～15 hours, and hydrogen flowing quantity is 10～150ml/g catalyzer .min.
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| CNB011314567A CN1152744C (en) | 2001-09-11 | 2001-09-11 | Process for preparing sec.-octanoly by hydrogenating sec.-octanone and its catalyst containing Ni |
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| CNB011314567A CN1152744C (en) | 2001-09-11 | 2001-09-11 | Process for preparing sec.-octanoly by hydrogenating sec.-octanone and its catalyst containing Ni |
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| CN102408305A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN102603473A (en) * | 2012-01-13 | 2012-07-25 | 河北科技大学 | Method for preparing corresponding alcohol through carbonyl compound selective hydrogenation |
| CN102746113A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of isopropanol |
| CN103071509A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof |
| CN103894207A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | High-dispersion type catalyst for liquid phase hydrogenation of octanol mixture, and preparation and application thereof |
| CN108774106A (en) * | 2018-06-13 | 2018-11-09 | 山东元利科技股份有限公司 | A kind of method and its catalyst for producing sec-octyl alcohol by extracting secondary octanone hydrogenating in thick sec-octyl alcohol |
| CN111215081A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Catalyst for preparing alcohols by aldehyde hydrogenation and preparation method thereof |
| CN111470943A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111468155A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111468125A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111470944A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111470945A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111468122A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111470942A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111468156A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN115974649A (en) * | 2022-12-28 | 2023-04-18 | 丰益高分子材料（连云港）有限公司 | Method for preparing sec-octanol |
-
2001
- 2001-09-11 CN CNB011314567A patent/CN1152744C/en not_active Expired - Fee Related
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102408305B (en) * | 2010-09-21 | 2014-04-02 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN102408305A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN102746113A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Preparation method of isopropanol |
| CN102746113B (en) * | 2011-04-20 | 2015-02-11 | 中国石油化工股份有限公司 | Preparation method of isopropanol |
| CN103071509A (en) * | 2011-10-26 | 2013-05-01 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof |
| CN103071509B (en) * | 2011-10-26 | 2014-11-05 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof |
| CN102603473A (en) * | 2012-01-13 | 2012-07-25 | 河北科技大学 | Method for preparing corresponding alcohol through carbonyl compound selective hydrogenation |
| CN103894207A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | High-dispersion type catalyst for liquid phase hydrogenation of octanol mixture, and preparation and application thereof |
| CN103894207B (en) * | 2012-12-27 | 2016-07-13 | 中国石油天然气股份有限公司 | A kind of capryl alcohol mixture liquid-phase hydrogenatin high dispersive type catalyst and preparation thereof and application |
| 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 |
| CN108774106A (en) * | 2018-06-13 | 2018-11-09 | 山东元利科技股份有限公司 | A kind of method and its catalyst for producing sec-octyl alcohol by extracting secondary octanone hydrogenating in thick sec-octyl alcohol |
| CN111215081A (en) * | 2018-11-26 | 2020-06-02 | 中国科学院大连化学物理研究所 | Catalyst for preparing alcohols by aldehyde hydrogenation and preparation method thereof |
| CN111468155A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111468125A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111470944A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111470945A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111468122A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111470942A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111468156A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN111470943A (en) * | 2019-01-23 | 2020-07-31 | 中国石油化工股份有限公司 | Synthetic method of alcohol compound |
| CN115974649A (en) * | 2022-12-28 | 2023-04-18 | 丰益高分子材料（连云港）有限公司 | Method for preparing sec-octanol |
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| CN1152744C (en) | 2004-06-09 |
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