CN101239315A - Catalyst for preparing 1,2-propylene glycol by glycerol hydrogenation and use thereof - Google Patents
Catalyst for preparing 1,2-propylene glycol by glycerol hydrogenation and use thereof Download PDFInfo
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- CN101239315A CN101239315A CNA2008100344263A CN200810034426A CN101239315A CN 101239315 A CN101239315 A CN 101239315A CN A2008100344263 A CNA2008100344263 A CN A2008100344263A CN 200810034426 A CN200810034426 A CN 200810034426A CN 101239315 A CN101239315 A CN 101239315A
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Abstract
The present invention provides a catalyst for preparing 1, 2-trimethylene glycol using glycerol and hydrogen, and its application. The catalyst precursors are prepared by coprecipitation method or immersion method, the constitute of non-oxygen element is Cu-Zr-A, A is one selected from titanium, tungsten or molybdenum, Cu is 4-40% by weight percentage composition of the catalyst precursors, A/Zr ratio is 0.1-10; the catalyst being reduction activation in hydrogen stream under 200-450 Celsius before being used. The catalyst shows excellent catalyzing effect in the preparing course of the 1, 2-trimethylene glycol using glycerol and hydrogen, and lower hydrogen pressure, reacting temperature, high selectivity and life.
Description
Technical field
The present invention relates to glycerine hydrogenation preparation 1, the catalyst of 2-propane diols, Preparation of catalysts method and the application in the glycerine hydrogenation reaction thereof.
Background technology
The shortage of world petroleum resource further goes up by oil price, and many countries are all in the substitute of actively seeking oil.Biodiesel is the regenerative resource of cleaning, it is the liquid fuel that raw material is made with oil plant water plant and animal fats such as oil-yielding shrubs fruit, engineering microalgaes such as oil crops such as soybean and rapeseed, oil palm and Chinese pistache, the food and drink wet goods that gives up, and is the petroleum diesel substitute of high-quality.But the biodiesel investment fever that heats up rapidly makes the glycerine of by-product in the production process surplus occur at present, and every production 1000 gram biodiesel produce 100 gram glycerine approximately.Therefore, seek the new new way of utilizing for these glycerine and caused the common concern in the whole world.
A kind of glycerine liquid-phase hydrogenatin preparation 1 has been described, the technology of 2-propane diols and ethylene glycol among the patent US 5214219.This process using CuO/ZnO/Al
2O
3Be catalyst, copper zinc atom ratio is 0.2～6, glycerol concentration 20～60%, and reaction temperature is more than 200 ℃, pressure 5～20MPa, glycerol conversion yield is 93% o'clock, 1, the high selectivity of 2-propane diols can reach 94%.But the glycerine material concentration that this patent adopts is lower, is 20～60% the aqueous solution, will cause the energy consumption of course of reaction higher.
Patent US 5616817 and CN 95121742.9 also adopt the liquid-phase hydrogenatin reaction process to produce 1 by glycerine, the 2-propane diols, employing contains the catalyst of Co, Cu, Mn, Mo and inorganic acid, glycerol concentration brings up to 86.5%, 210～220 ℃ of reaction temperatures, pressure 29.5MPa is under glycerine 100% transforms, 1, the high selectivity of 2-propane diols reaches 95%.But this method Hydrogen Vapor Pressure is too high, will increase the cost of investment and the operation easier of device.
Missouri, USA university research group development gone out the glycerine two-step process (Appliedcatalysis A:General, 282 (2005), 225-231).Glycerine at first dewaters and obtains hydroxypropanone-, and hydrogenation obtains 1 then, and the 2-propane diols is a catalyst with the copper chromite, glycerol concentration 80 weight %, 200 ℃ of reaction temperatures, pressure 1～2MPa, glycerol conversion yield 46.6%, 1,2-propane diols selectivity 85%.Though reaction pressure reduces greatly, the method adopts two step still formula hydrogenation reaction technologies, and long flow path and product and catalyst are not easily separated, and gathering of accessory substance also causes catalyst life not long.
Reported a kind of technology of glycerine gas phase hydrogenation among the patent WO2007/010299 of Davy company application.This process using Cu series catalysts, raw material is the methanol solution of glycerine, 160～260 ℃ of reaction temperatures, pressure 1～3MPa, hydrogen and glycerine ratio 400: 1～600: 1, the time of staying 0.3～1.5s.It is said,, can optionally produce 1,2-propane diols and propyl alcohol by adjusting catalyst and technological parameter.Under glycerine 100% transforms, 1,2-propane diols selectivity can reach 96%.But, adopt gaseous state glycerine and high hydrogen glycerine ratio in this patent, make energy consumption higher, and increase considerably the operating cost of device, because of glycerine boiling point height, its gasification certainly will be caused the partial glycerol coking, and influence the production unit consumption in addition.
Chinese patent CN200710043082.8 discloses a kind of ternary compound oxides catalyst and has been used for glycerine hydrogenation preparation 1, the method of 2-propane diols, but this method is not set forth the Preparation of catalysts method, and adopted less hydrogen and glycerine than (3: 1～15: 1), make reaction temperature height, reaction heat not to remove fast, cause accessory substance to increase, will shorten the service life of catalyst.
There are problems such as reaction pressure is big, operating cost is high, catalyst life is short at glycerine hydrogenation technology in the above-mentioned patent, the present invention adopts trickle bed liquid-phase catalysis reaction process, with highly active Cu-Zr-A is catalyst, has that material concentration height, hydrogen pressure are low, hydrogen and the glycerine mol ratio is moderate, reaction temperature is low, selectivity is high, the life-span is long characteristics.
Summary of the invention
The technical problem to be solved in the present invention provides and a kind ofly prepares 1 efficiently by the glycerine liquid phase catalytic hydrogenation, the method for 2-propane diols.
Glycerine liquid-phase hydrogenatin preparation 1, the 2-propane diols is implemented by following technical solution:
Catalyst precursor is a kind of composite oxides, is to adopt coprecipitation or immersion process for preparing, and its nonoxygen element consists of Cu-Zr-A, and wherein A is a kind of in titanium, tungsten or the molybdenum; The weight percentage that copper accounts for catalyst precursor is 4～40%, and the preferred weight percentage composition is 10～30%; The A/Zr atomic ratio is 0.1～10, preferred 0.2～5.0.
The raw material that coprecipitation prepares the catalyst precursor is: the copper source is copper nitrate, Schweinfurt green or copper chloride, and the zirconium source is zirconium oxychloride, zirconium nitrate or zirconium alkoxide, and the titanium source is titanium sulfate titanium tetrachloride or alkoxytitanium, and the tungsten source is an ammonium metatungstate, and the molybdenum source is an ammonium molybdate.Preparation process is: at first copper source and the zirconium source compound with metering adds in the entry successively with the titanium source or with the tungsten source or with the molybdenum source compound and mixes, and adds surfactant polyethylene or polyvinyl alcohol again; Under 40～80 ℃ of strong agitation, drip weight percent content then and be 20～40% ammoniacal liquor, reach 7.0～8.0, form slurries until the pH value; Slurries after the drying, are obtained catalyst precursor in 350～600 ℃ of roastings in 120 ℃ of baking ovens.
The raw material of immersion process for preparing catalyst precursor is: the copper source is copper nitrate, Schweinfurt green or copper chloride, and the zirconium source is a zirconia, and the titanium source is zirconia (titanium dioxide or a rutile), and the tungsten source is a tungsten oxide, and the molybdenum source is a molybdenum oxide.The process of immersion process for preparing catalyst precursor is: at first the zirconia of metering and titanium oxide or tungsten oxide or molybdenum oxide powder are mixed, flood the copper source aqueous solution of metering then, after the drying, roasting obtains catalyst precursor in 350～600 ℃ of air streams.
The catalyst precursor of above-mentioned two kinds of methods preparation needs to carry out reduction activation and handles in hydrogen stream, the hydrogen reducing condition is: 200～450 ℃ of temperature, pressure 1.0～5.0MPa, hydrogen gas space velocity 100～1000h
-1, 1～10 hour recovery time.Catalyst through hydrogen reducing activation preparation is used to the glycerine hydrogenation reaction, hydrogenation reaction adopts trickle bed liquid-phase hydrogenatin technology, and reaction condition is: glycerine weight percent concentration 20～100%, 150～300 ℃ of reaction temperatures, pressure 1～20MPa, liquid air speed are 0.2～4.0h
-1, hydrogen and glycerine mol ratio 2～400, preferred reaction condition is: glycerine weight percent concentration 60～90%, 180～250 ℃ of reaction temperatures, pressure 3.0～8.0MPa, liquid air speed are 0.4～2.0h
-1, hydrogen and glycerine mol ratio 10～100.
This technology has the advantages that hydrogen pressure is low, reaction temperature is low, selectivity is high, the life-span is long.Use this technology to carry out glycerine hydrogenation, can effectively solve the deficiency that exists in the existing technology.
The specific embodiment
Below by embodiment the present invention is further described, but protection domain is not subjected to the restriction of embodiment.
Embodiment 1
178.1g zirconium oxychloride, 39.0g ammonium molybdate, 15.2g copper nitrate, 2.0g polyethylene glycol are added in the 1000ml water successively, also continue under the stirring at 70 ℃, ammoniacal liquor to the pH value that drips 30 weight % reaches 7.0, obtains slurries.Slurries obtain catalyst precursor 500 ℃ of roastings after 120 ℃ of dryings.The weight percentage that Cu accounts for catalyst precursor is 4%, and A/Zr (atomic ratio) is 0.4 (the catalyst composition sees Table 1).
Catalytic reaction adopts trickle bed reactor, loaded catalyst 7.5g, and fill with quartz sand at two ends.Before catalyst uses at 260 ℃, 2.0MPa and air speed 500h
-1Condition under logical hydrogen reducing handle 8h.Weight percent concentration is that 60% glycerite enters reactor and carries out hydrogenation reaction after 150 ℃ of preheatings, and reaction condition is: Hydrogen Vapor Pressure 6.0MPa, 220 ℃ of temperature, H
2/ glycerine mol ratio 50, liquid air speed 1.0h
-1Enter gas-liquid separator after the hydrogenation products cooling, product liquid is analyzed (the results are shown in Table 2) by gas-chromatography.
Embodiment 2-6
Preparation of Catalyst is with embodiment 1, and difference is that Cu accounts for the weight percentage difference of catalyst precursor.Catalytic component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 7-11
Preparation of Catalyst is with embodiment 3, and difference is A/Zr (atomic ratio) difference.Catalytic component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 12
With 14.7g zirconia, 6.9g molybdenum oxide mixed grinding, obtain compound at 550 ℃ of roasting 8h, flood the aqueous solution that 400ml contains the 15.2g copper nitrate then, after the drying, obtain catalyst precursor 550 ℃ of roastings.The weight percentage that Cu accounts for catalyst precursor is 15%, and A/Zr (atomic ratio) is 0.4.
Catalytic component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 13
With 12.3g zirconia, 9.3g tungsten oxide mixed grinding, obtain compound at 600 ℃ of roasting 8h, flood the aqueous solution that 400ml contains the 15.2g copper nitrate then, after the drying, obtain catalyst precursor 550 ℃ of roastings.The weight percentage that Cu accounts for catalyst precursor is 15%, and A/Zr (atomic ratio) is 0.4.
Catalytic component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 14
55.3g zirconium oxychloride, 11.0g titanium sulfate, 15.2g copper nitrate, 2.0g polyethylene glycol are added in the 1000ml water successively, also continue under the stirring at 70 ℃, ammoniacal liquor to the pH value of dropping 30% reaches 7.0, obtains slurries.Slurries are after 120 ℃ of dryings, and 500 ℃ of roastings obtain catalyst precursor.The weight percentage that Cu accounts for catalyst precursor is 15%, and A/Zr (atomic ratio) is 0.4.
Catalytic component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 15
39.8g zirconium oxychloride, 13.5g ammonium metatungstate, 15.2g copper nitrate, 2.0g polyethylene glycol are added in the 1000ml water successively, also continue under the stirring at 70 ℃, ammoniacal liquor to the pH value that drips 30 weight % reaches 7.0, obtains slurries.Slurries are after 120 ℃ of dryings, and 500 ℃ of roastings obtain catalyst precursor.The weight percentage that Cu accounts for catalyst precursor is 15%, and A/Zr (atomic ratio) is 0.4.
Catalytic component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 16-24
Preparation of Catalyst and course of reaction are with embodiment 3, and difference is glycerine hydrogenation reaction condition difference.Catalytic component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 25
Catalyst and reaction condition are investigated its stability with embodiment 3.Catalytic component sees Table 1, hydrogenation conditions and the results are shown in Table 3.
Each embodiment catalyst precursor preparation condition of table 1 and nonoxygen element Cu-Zr-A form
| Embodiment | Cu-Zr-A forms | The preparation method | The copper source compound | The zirconium source compound | The A source compound | Cu weight % | A/Zr (atomic ratio) |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 | Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-W Cu-Zr-Ti Cu-Zr-W Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo Cu-Zr-Mo | Co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation infusion process infusion process co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation co-precipitation | Copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate copper nitrate | Zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconia zirconia zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride | Ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate molybdenum oxide tungsten oxide titanium sulfate ammonium metatungstate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate ammonium paramolybdate | 4 10 15 20 25 30 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 15 | 0.4 0.4 0.4 0.4 0.4 0.4 0.3 0.6 1.0 2.0 5.0 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 |
Glycerine hydrogenation reaction condition and the result of each embodiment of table 2
| Embodiment | Glycerol concentration (weight %) | Reaction temperature (℃) | Reaction pressure (MPa) | H 2/ glycerine mol ratio | Air speed (h -1) | Conversion ratio (%) | Selectivity (%) |
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 | 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 40 80 90 60 60 60 60 60 60 | 220 220 220 220 220 220 220 220 220 220 220 220 200 220 210 220 220 220 220 220 230 210 240 250 | 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 3.0 10 15 6.0 6.0 6.0 | 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 20 100 200 | 1.0 1.0 1.0 0.5 1.0 1.5 1.0 1.0 1.0 1.0 1.0 1.5 2.0 1.0 2.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 | 60.0 80.0 99.0 99.0 90.0 80.0 94.0 97.0 92.0 90.2 88.5 85.6 82.3 92.0 84.0 100.0 98.5 94.6 96.5 100.0 100.0 94.5 100.0 100.0 | 95.0 95.5 95.0 95.9 95.0 95.0 95.2 95.2 94.6 95.3 94.7 95.3 94.8 95.1 95.2 95.6 95.8 96.0 95.4 96.0 95.5 96.2 96.4 96.3 |
The study on the stability situation of table 3 embodiment 3 catalyst
| Reaction time (h) | Glycerol concentration (weight %) | Reaction temperature (℃) | Reaction pressure (MPa) | H 2/ glycerine mol ratio | Air speed (h -1) | Conversion ratio (%) | Selectivity (%) |
| 50 100 150 300 400 | 60 60 60 60 60 | 220 220 220 220 220 | 6.0 6.0 6.0 6.0 6.0 | 50 50 50 50 50 | 1.0 1.0 1.0 1.0 1.0 | 99.0 98.5 99.2 99.1 98.8 | 95.0 94.8 95.2 95.0 95.0 |
Claims (7)
1, a kind of glycerine hydrogenation preparation 1, the catalyst of 2-propane diols, it is characterized in that adopting coprecipitation or immersion process for preparing catalyst precursor, catalyst precursor is composite oxides, its nonoxygen element consists of Cu-Zr-A, wherein A is selected from a kind of in titanium, tungsten or the molybdenum, and the weight percent content that Cu accounts for catalyst precursor is 4～40%, and the A/Zr atomic ratio is 0.1～10; This catalyst precursor carries out reduction activation in 200～450 ℃ hydrogen stream, make to be used for glycerine hydrogenation preparation 1, the catalyst of 2-propane diols.
2, according to the described catalyst of claim 1, it is characterized in that the weight percentage that Cu in the described catalyst precursor accounts for catalyst precursor is 10～30%, the A/Zr atomic ratio is 0.2～5.0.
3, according to the described catalyst of claim 1, it is characterized in that the raw material that coprecipitation prepares catalyst precursor is: the copper source is copper nitrate, Schweinfurt green or copper chloride, the zirconium source is zirconium oxychloride, zirconium nitrate or zirconium alkoxide, the titanium source is titanium sulfate, titanium tetrachloride or alkoxytitanium, the tungsten source is an ammonium metatungstate, and the molybdenum source is an ammonium paramolybdate; The process that coprecipitation prepares catalyst precursor is: at first copper source and the zirconium source compound with metering adds in the entry successively with the titanium source or with the tungsten source or with the molybdenum source compound and mixes, add surfactant polyethylene or polyvinyl alcohol again, under 40～80 ℃ of strong agitation, drip weight percent content then and be 20～40% ammoniacal liquor, reach 7.0～8.0 and form slurries until the pH value, after the drying, roasting obtains catalyst precursor to these slurries in 350～600 ℃ of air streams in 120 ℃ of baking ovens.
4, according to the described catalyst of claim 1, it is characterized in that the raw material of immersion process for preparing catalyst precursor is: the copper source is copper nitrate, Schweinfurt green or copper chloride, and the zirconium source is a zirconia, and the titanium source is titanium dioxide or rutile, and the tungsten source is a tungsten oxide, and the molybdenum source is a molybdenum oxide; The process of immersion process for preparing catalyst precursor is: at first the zirconia of metering and titanium oxide or tungsten oxide or molybdenum oxide powder are mixed, flood the copper source aqueous solution of metering then, after the drying, roasting obtains catalyst precursor in 350～600 ℃ of air streams.
5, according to the described catalyst of claim 1, it is characterized in that catalyst precursor is used for glycerine hydrogenation preparation 1 by hydrogen reducing activation preparation, the catalyst of 2-propane diols, the hydrogen reducing activation condition is: 200～450 ℃ of temperature, pressure 1.0～5.0MPa, hydrogen gas space velocity 100～1000h
-1, 1～10 hour recovery time.
6, Application of Catalyst according to claim 1 or 5, it is characterized in that catalyst is used for glycerine hydrogenation preparation 1, the reaction condition of 2-propane diols is: the glycerine weight percent concentration is 20～100%, the hydrogenation reaction temperature is 150～300 ℃, pressure is 1～20MPa, and the liquid air speed is 2.0-4.0h
-1, hydrogen and glycerine mol ratio are 2～400.
7, Application of Catalyst according to claim 1 or 5, it is characterized in that catalyst is used for glycerine hydrogenation preparation 1, the reaction condition of 2-propane diols is: the glycerine weight percent concentration is 60～90%, the hydrogenation reaction temperature is 180～250 ℃, pressure 3.0～8.0Mpa, the liquid air speed is 0.4～2.0h
-1, hydrogen and glycerine mol ratio are 10～100.
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| CN101767006A (en) * | 2008-12-30 | 2010-07-07 | 拜耳技术工程（上海）有限公司 | Catalyst for preparing fatty alcohol with low carbon number by catalyzing and hydrolyzing glycerol and preparation method thereof |
| CN102264680A (en) * | 2008-12-23 | 2011-11-30 | 环球油品公司 | Method for converting glycerol to propanol |
| CN102924233A (en) * | 2012-10-20 | 2013-02-13 | 青岛科技大学 | Method for preparing propylene glycol by glycerin hydrogenolysis |
| WO2014134733A1 (en) * | 2013-03-07 | 2014-09-12 | University Of Saskatchewan | Process for hydrogenolysis of glycerol |
| CN107376932A (en) * | 2017-04-13 | 2017-11-24 | 山东昆达生物科技有限公司 | A kind of copper-based hydrogenation catalyst and preparation method thereof and prepare the method for oxinane using it |
| CN110026202A (en) * | 2019-05-21 | 2019-07-19 | 北京石油化工学院 | Glycerine hydrogenation catalyst, catalyst precursor and the preparation method and application thereof |
| CN112090424A (en) * | 2020-08-18 | 2020-12-18 | 北京石油化工学院 | Catalyst for preparing 1, 2-propylene glycol by glycerol hydrogenolysis, preparation method thereof and method for preparing 1, 2-propylene glycol by glycerol hydrogenolysis |
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| CN102264680A (en) * | 2008-12-23 | 2011-11-30 | 环球油品公司 | Method for converting glycerol to propanol |
| CN101767006A (en) * | 2008-12-30 | 2010-07-07 | 拜耳技术工程（上海）有限公司 | Catalyst for preparing fatty alcohol with low carbon number by catalyzing and hydrolyzing glycerol and preparation method thereof |
| CN101767006B (en) * | 2008-12-30 | 2013-04-03 | 拜耳技术工程（上海）有限公司 | Catalyst for preparing fatty alcohol with low carbon number by catalyzing and hydrolyzing glycerol and preparation method thereof |
| CN102924233A (en) * | 2012-10-20 | 2013-02-13 | 青岛科技大学 | Method for preparing propylene glycol by glycerin hydrogenolysis |
| CN102924233B (en) * | 2012-10-20 | 2015-04-15 | 青岛科技大学 | Method for preparing propylene glycol by glycerin hydrogenolysis |
| WO2014134733A1 (en) * | 2013-03-07 | 2014-09-12 | University Of Saskatchewan | Process for hydrogenolysis of glycerol |
| CN107376932A (en) * | 2017-04-13 | 2017-11-24 | 山东昆达生物科技有限公司 | A kind of copper-based hydrogenation catalyst and preparation method thereof and prepare the method for oxinane using it |
| CN107376932B (en) * | 2017-04-13 | 2020-06-12 | 山东昆达生物科技有限公司 | Copper-based hydrogenation catalyst, preparation method thereof and method for preparing tetrahydropyran by using copper-based hydrogenation catalyst |
| CN110026202A (en) * | 2019-05-21 | 2019-07-19 | 北京石油化工学院 | Glycerine hydrogenation catalyst, catalyst precursor and the preparation method and application thereof |
| CN112090424A (en) * | 2020-08-18 | 2020-12-18 | 北京石油化工学院 | Catalyst for preparing 1, 2-propylene glycol by glycerol hydrogenolysis, preparation method thereof and method for preparing 1, 2-propylene glycol by glycerol hydrogenolysis |
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