CN101270032A - Method for preparing 1,5-pentanediol - Google Patents
Method for preparing 1,5-pentanediol Download PDFInfo
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- CN101270032A CN101270032A CNA2008100360887A CN200810036088A CN101270032A CN 101270032 A CN101270032 A CN 101270032A CN A2008100360887 A CNA2008100360887 A CN A2008100360887A CN 200810036088 A CN200810036088 A CN 200810036088A CN 101270032 A CN101270032 A CN 101270032A
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- glutaraldehyde
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- pentanediol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The present invention relates to a method used for preparing 1, 5-pentanediol with hydrogenation of 1, 5-glutaraldehyde. In the method, Ru is used as the load catalyst of active components; the weight percent of the Ru in the catalyst is 0.2 percent to 10 percent; the carrier is a molecular sieve, or one of or the mixture of Al2O3, SiO2, TiO2, MgO, amorphous aluminosilicate and activated carbon. When the 1, 5-glutaraldehyde is hydrogenated to prepare the 1, 5-pentanediol, the reaction conditions are mild; the catalyst has high activity; and the method is an effective way for preparing the 1, 5-pentanediol.
Description
Technical field
The present invention relates to a kind of 1,5-glutaraldehyde hydrogenation preparing 1, the method for 5-pentanediol specifically comprises 1,5-glutaraldehyde hydrogenation preparing 1, the catalyzer of 5-pentanediol and reaction process.
Background technology
1, the 5-pentanediol is a kind of broad-spectrum chemical, can directly be used as the solvent or the wetting agent of machining oil, special washing composition, emulsion paint, also can be used as the raw material of producing new polyester, coating, tackiness agent, sealing agent, softening agent etc.Its production method mainly contains following four kinds: 1) made 300～330 ℃ of temperature of reaction, reaction pressure 22～42MPa by the tetrahydrofurfuryl alcohol shortening.This method reaction pressure height has increased facility investment and operation easier; 2) the epoxy pentenol that is made by cyclopentadiene photoxidation hydrogenation under 70～100 ℃ and about 6MPa pressure makes.Cyclopentadiene photoxidation yield is low, and the economy of whole process is relatively poor; 3) Chinese patent CN1565728A has described 1, the 5-Methyl glutarate under the CuZnAl catalyst effect under 150～350 ℃ and 3～5MPa hydrogenation preparing 1, the method for 5-pentanediol, 1,5-Methyl glutarate transformation efficiency is greater than 95%, 1, and 5-pentanediol selectivity is greater than 95%.But this method is starting raw material with the pentanedioic acid, the middle need through reactions steps such as over-churnings, and flow process is longer.4) Chinese patent CN1072168A has reported with the ethyl vinyl ether of replacement and the acrolein reaction of replacement, 3 of generation replacement, and the 4-dihydropyrane, 3 of replacement, 4-dihydropyrane acid-catalyzed hydrolysis generates the glutaraldehyde that replaces, then the pentanediol of hydrogenation generation replacement.The hydrogenation catalyst that this patent is mentioned is raney nickel or modification raney nickel, the perhaps aluminum oxide of load platinum, palladium or nickel.
Summary of the invention
The object of the present invention is to provide a kind of 1,5-glutaraldehyde hydrogenation preparing 1, the method of 5-pentanediol, it is the loaded catalyst of active ingredient that this method adopts with Ru, this catalyzer is used for 1,5-glutaraldehyde hydrogenation preparing 1,5-pentanediol when reaction, active, selectivity is high, the reaction conditions gentleness, for preparing 1, the 5-pentanediol provides a kind of new effective way.
The present invention is achieved by the following technical solutions:
A kind of 1,5-glutaraldehyde hydrogenation preparing 1, the method of 5-pentanediol, this method is to be solvent with a kind of in water, methyl alcohol, ethanol or the Virahol or they with arbitrary proportion blended mixture, with massfraction be 5%～80% 1, the 5-glutaraldehyde solution is a raw material, adopting Ru is the loaded catalyst of active ingredient, by gas-liquid-solid three-phase catalytic hydrogenation reaction preparation 1,5-pentanediol.The reactive mode that adopts is selected intermittently still reaction or continuous fixed bed reaction or continuous, and loading type Ru support of the catalyst is molecular sieve or Al
2O
3, SiO
2, TiO
2, a kind of in MgO, amorphous aluminum silicate or the activated carbon or they are with arbitrary proportion blended mixture, are preferably hydrogen type molecular sieve HZSM-5, HMCM-49, HSAPO-34, HMOR, H β or γ-Al
2O
3, SiO
2, any in the activated carbon or their mixture.To account for the massfraction of catalyzer total amount be 0.2%～10% to active ingredient Ru in the loading type Ru catalyzer, preferred 0.5%～6%.
Loading type Ru catalyzer adopts immersion process for preparing, be with the soluble salt of ruthenium or complex solution by metering than flooding in the support of the catalyst that adds moulding in advance, carry out drying and roasting then and make; This catalyzer needs to reduce processing with hydrogen before use, and reductive condition is hydrogen pressure 0.2～10.0MPa, hydrogen gas space velocity 200～1500h
-1, 180～400 ℃ of reduction temperatures, recovery time 1～24h, preferred reductive condition is hydrogen pressure 2.0～8.0MPa, hydrogen gas space velocity 300～800h
-1, 200～350 ℃ of reduction temperatures, recovery time 4～20h.
1,5-glutaraldehyde hydrogenation preparing 1, the reactive mode that the 5-pentanediol adopts can be selected intermittently still reaction, also can select continuous fixed bed reaction or continuous.Batch still formula reaction conditions is: with a kind of in water, methyl alcohol, ethanol or the Virahol or they mixture as solvent with arbitrary proportion, raw material 1, the massfraction of 5-glutaraldehyde solution are 5%～80%, 50～160 ℃ of temperature of reaction, reaction pressure 0.5～15.0MPa, reaction times 1～24h; Preferred reaction conditions is: raw material 1, the massfraction of 5-glutaraldehyde solution are 10%～50%, 60～120 ℃ of temperature of reaction, reaction pressure 2.0～8.0MPa, reaction times 2～8h.The continuous fixed bed reaction or continuous condition is: with a kind of in water, methyl alcohol, ethanol or the Virahol or they mixture as solvent with arbitrary proportion, raw material 1, the massfraction 5%～80% of 5-glutaraldehyde solution, 50～160 ℃ of temperature of reaction, reaction pressure 0.5～15.0MPa, raw material 1,5-glutaraldehyde solution air speed 0.5～10.0h
-1, H
2/ 1,5-glutaraldehyde mol ratio 1: 1～100: 1; Preferred reaction conditions is: raw material 1,5-glutaraldehyde massfraction 10%～50%, 60～120 ℃ of temperature of reaction, reaction pressure 2.0～8.0MPa, 1,5-glutaraldehyde solution air speed 1.0～8.0h
-1, H
2/ 1,5-glutaraldehyde mol ratio 3: 1～20: 1.
Embodiment
To come the present invention is illustrated with specific embodiment below, but protection domain of the present invention be not limited to these embodiment.
Embodiment 1-8
Preparation of catalysts: prepare certain density RuCl
3The aqueous solution floods than adding in the support of the catalyst according to metering, then 110 ℃ dry 12 hours down, 450 ℃ of N
2Roasting is 4 hours under the atmosphere.Reduce to room temperature after roasting finishes, in the reactor of packing into,, after reduction finishes condition adjusted to the required condition of reaction with 300 ℃ of hydrogen reduction 4 hours.The catalyzer composition sees Table 1 among each embodiment.
Table 1.
| Embodiment | Carrier | The quality percentage composition of Ru, % |
| Embodiment 1 | Hβ | 2.0 |
| Embodiment 2 | γ-Al 2O 3 | 3.2 |
| Embodiment 3 | SiO 2 | 2.5 |
| Embodiment 4 | Coal-based activated carbon | 3.4 |
| Embodiment 5 | HMOR | 3.5 |
| Embodiment 6 | Cocos active carbon | 2.5 |
| Embodiment 7 | HMCM-49 | 4.5 |
| Embodiment 8 | Amorphous silicon aluminium | 4.5 |
The reactive behavior evaluation of catalyzer: in 500 milliliters of stainless steel high pressure stirred autoclaves, add 300 gram mass marks respectively and be 20% 1, a kind of in the catalyzer of 5-glutaraldehyde solution and a certain amount of (based on reaction raw materials) embodiment 1～4, be warming up to temperature of reaction behind the hydrogen exchange reactor, 90～110 ℃ of control reaction pressure 1.0～5.0MPa, temperature of reaction, stirring velocity 1000 is changeed.Reaction conditions and reaction result concrete among the embodiment 1～4 see Table 2.
Table 2.
| Embodiment | Solvent | Temperature of reaction, ℃ | Reaction pressure, MPa | Reaction times, h | The catalyzer add-on, % (quality) | The glutaraldehyde transformation efficiency, % | The pentanediol selectivity, % |
| 1 | Water | 90 | 1.0 | 4 | 2.0 | 95.6 | 92.5 |
| 2 | Water | 95 | 2.0 | 6 | 2.0 | 96.5 | 89.5 |
| 3 | Ethanol | 100 | 5.0 | 6 | 3.0 | 88.3 | 92.6 |
| 4 | Virahol | 95 | 5.0 | 4 | 3.0 | 100 | 95.5 |
Catalyzer among the embodiment 5～8 100 gram is respectively charged into fixed-bed tube reactor, and 300 ℃ with hydrogen reducing 4 hours, and reduction is cooled to temperature of reaction after finishing.Massfraction be 25% 1, enter reactor reaction after 5-glutaraldehyde solution and the hydrogen mixing preheating, concrete reaction conditions and reaction result see Table 3 among the embodiment 5～8.
Table 3.
| Embodiment | Solvent | Temperature of reaction, ℃ | Reaction pressure, MPa | The glutaraldehyde solution air speed, h -1 | The glutaraldehyde transformation efficiency, % | The pentanediol selectivity, % |
| 5 | Water | 95 | 5.0 | 1.0 | 95.2 | 98.3 |
| 6 | Water | 100 | 5.0 | 2.0 | 100 | 98.5 |
| 7 | Ethanol | 100 | 5.0 | 1.5 | 92.6 | 88.5 |
| 8 | Virahol | 110 | 5.0 | 2.5 | 96.4 | 93.8 |
Claims (6)
1, a kind of 1, the preparation method of 5-pentanediol, it is characterized in that this method is is solvent with a kind of in water, methyl alcohol, ethanol or the Virahol or they with arbitrary proportion blended mixture, with massfraction be 5%～80% 1, the 5-glutaraldehyde solution is a raw material, and adopting Ru is the loading type Ru catalyzer of active ingredient, by gas-liquid-solid three-phase catalytic hydrogenation reaction preparation 1,5-pentanediol, the reactive mode of employing are selected intermittently still reaction or continuous fixed bed reaction or continuous; Loading type Ru support of the catalyst is molecular sieve or Al
2O
3, SiO
2, TiO
2, a kind of in MgO, amorphous aluminum silicate or the activated carbon or they are with arbitrary proportion blended mixture; The batch still formula is reflected at 50～160 ℃ of temperature and pressure 0.5～15.0MPa reacted 1～24 hour down; The reaction conditions of continuous fixed bed reaction or continuous is 50～160 ℃ of temperature of reaction, reaction pressure 0.5～15.0MPa, 1,5-glutaraldehyde solution air speed 0.5～10.0h
-1, H
2/ 1,5-glutaraldehyde mol ratio 1: 1～100: 1.
2, method according to claim 1 is characterized in that loading type Ru support of the catalyst is hydrogen type molecular sieve HZSM-5, HMCM-49, HSAPO-34, HMOR, H β or γ-Al
2O
3, SiO
2, any or they in the activated carbon mixture.
3, method according to claim 1, it is characterized in that loading type Ru catalyzer adopts immersion process for preparing, be with the soluble salt of ruthenium or complex solution by metering than flooding in the support of the catalyst that adds moulding in advance, carry out drying and roasting then and make, to account for the massfraction of catalyzer total amount be 0.2%～10% to Ru in the catalyzer; This catalyzer needs to reduce processing with hydrogen before use, and reductive condition is hydrogen pressure 0.2～10.0MPa, hydrogen gas space velocity 200～1500h
-1, 180～400 ℃ of reduction temperatures, 1～24 hour recovery time.
4, method according to claim 3 is characterized in that the massfraction that Ru in the loading type Ru catalyzer accounts for the catalyzer total amount is 0.5%～6%, and the reductive condition of catalyzer is hydrogen pressure 2.0～8.0MPa, hydrogen gas space velocity 300～800h
-1, 200～350 ℃ of reduction temperatures, 4～20 hours recovery times.
5, method according to claim 1, it is characterized in that loading type Ru catalyzer is used for 1,5-glutaraldehyde hydrogenation system 1, the batch still formula reaction conditions of 5-pentanediol is: 1, and 5-glutaraldehyde massfraction is 10%～50%, 60～120 ℃ of temperature of reaction, reaction pressure 2.0～8.0MPa, 2～8 hours reaction times.
6, method according to claim 1, it is characterized in that loading type Ru catalyzer is used for 1,5-glutaraldehyde hydrogenation system 1, the continuous fixed bed reaction or continuous condition of 5-pentanediol is: 1,5-glutaraldehyde massfraction is 10%～50%, 60～120 ℃ of temperature of reaction, reaction pressure 2.0～8.0MPa, 1, and 5-glutaraldehyde solution air speed is 1.0～8.0h
-1, H
2/ 1,5-glutaraldehyde mol ratio is 3: 1～20: 1.
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|---|---|---|---|
| CN2008100360887A CN101270032B (en) | 2008-04-16 | 2008-04-16 | Method for preparing 1,5-pentanediol |
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|---|---|---|---|
| CN2008100360887A CN101270032B (en) | 2008-04-16 | 2008-04-16 | Method for preparing 1,5-pentanediol |
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| CN101270032B CN101270032B (en) | 2011-07-27 |
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Cited By (9)
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| CN101890361A (en) * | 2010-07-27 | 2010-11-24 | 万华实业集团有限公司 | Catalyst for use in highly selective preparation of gasoline fractions from synthesis gas and preparation method thereof |
| CN103111318A (en) * | 2013-03-01 | 2013-05-22 | 江苏九九久科技股份有限公司 | Supported catalyst with ruthenium (III) as active center and preparation method of catalyst |
| CN105289592A (en) * | 2015-11-19 | 2016-02-03 | 中科合成油技术有限公司 | Method for preparing gamma-valerolactone by acetylpropionic acid catalytic hydrogenation |
| CN106622219A (en) * | 2016-10-28 | 2017-05-10 | 南京工业大学 | Catalyst for preparing tetrahydrofurfuryl alcohol by furfuralcohol liquid phase hydrogenation, preparation method and application thereof |
| CN106881085A (en) * | 2017-03-16 | 2017-06-23 | 兰州理工大学 | The catalyst and preparation method and process for selective hydrogenation of hydroquinones hydrogenation |
| WO2018170932A1 (en) | 2017-03-23 | 2018-09-27 | 万华化学集团股份有限公司 | Catalyst for preparing 1,5-pentanediol via hydrogenolysis of tetrahydrofurfuryl alcohol, method and application thereof |
| CN111097424A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Method for preparing 1, 5-pentanediol through liquid phase hydrogenation based on modified palladium supported catalyst |
| CN113860989A (en) * | 2021-11-08 | 2021-12-31 | 中国天辰工程有限公司 | Synthesis method of 1, 6-hexanediol |
| CN113943207A (en) * | 2021-11-23 | 2022-01-18 | 中国成达工程有限公司 | Process for synthesizing butanediol by hydrogenation of succinaldehyde |
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| DE19860489B4 (en) * | 1998-12-28 | 2008-05-08 | Basf Ag | A process for the hydrogenation of aldehydes and use of a catalyst for the reduction of an aldehyde to an alcohol |
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2008
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| CN101890361A (en) * | 2010-07-27 | 2010-11-24 | 万华实业集团有限公司 | Catalyst for use in highly selective preparation of gasoline fractions from synthesis gas and preparation method thereof |
| CN101890361B (en) * | 2010-07-27 | 2013-04-24 | 万华实业集团有限公司 | Preparation method of catalyst for use in highly selective preparation of gasoline fractions from synthesis gas |
| CN103111318A (en) * | 2013-03-01 | 2013-05-22 | 江苏九九久科技股份有限公司 | Supported catalyst with ruthenium (III) as active center and preparation method of catalyst |
| CN105289592B (en) * | 2015-11-19 | 2017-11-28 | 中科合成油技术有限公司 | It is catalyzed method of the levulic acid Hydrogenation for γ valerolactones |
| CN105289592A (en) * | 2015-11-19 | 2016-02-03 | 中科合成油技术有限公司 | Method for preparing gamma-valerolactone by acetylpropionic acid catalytic hydrogenation |
| CN106622219A (en) * | 2016-10-28 | 2017-05-10 | 南京工业大学 | Catalyst for preparing tetrahydrofurfuryl alcohol by furfuralcohol liquid phase hydrogenation, preparation method and application thereof |
| CN106622219B (en) * | 2016-10-28 | 2019-11-08 | 南京工业大学 | Catalyst for preparing tetrahydrofurfuryl alcohol by furfuralcohol liquid phase hydrogenation, preparation method and application thereof |
| CN106881085A (en) * | 2017-03-16 | 2017-06-23 | 兰州理工大学 | The catalyst and preparation method and process for selective hydrogenation of hydroquinones hydrogenation |
| WO2018170932A1 (en) | 2017-03-23 | 2018-09-27 | 万华化学集团股份有限公司 | Catalyst for preparing 1,5-pentanediol via hydrogenolysis of tetrahydrofurfuryl alcohol, method and application thereof |
| US10974233B2 (en) | 2017-03-23 | 2021-04-13 | Wanhua Chemical Group Co., Ltd. | Catalyst for preparing 1,5-pentanediol via hydrogenolysis of tetrahydrofurfuryl alcohol, method and application thereof |
| CN111097424A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Method for preparing 1, 5-pentanediol through liquid phase hydrogenation based on modified palladium supported catalyst |
| CN111097424B (en) * | 2018-10-25 | 2024-01-26 | 中国石油化工股份有限公司 | Method for preparing 1, 5-pentanediol by liquid phase hydrogenation based on modified palladium supported catalyst |
| CN113860989A (en) * | 2021-11-08 | 2021-12-31 | 中国天辰工程有限公司 | Synthesis method of 1, 6-hexanediol |
| CN113860989B (en) * | 2021-11-08 | 2024-04-16 | 中国天辰工程有限公司 | Synthesis method of 1, 6-hexanediol |
| CN113943207A (en) * | 2021-11-23 | 2022-01-18 | 中国成达工程有限公司 | Process for synthesizing butanediol by hydrogenation of succinaldehyde |
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| CN101270032B (en) | 2011-07-27 |
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Effective date of registration: 20170215 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |