CN101239315B - 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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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 catalyzer of 2-propylene glycol, 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.Biofuel is the renewable energy source of cleaning, it is the liquid fuel that raw material is made with oil plant waterplant and animal grease such as oil-yielding shrubs fruit, engineering microalgaes such as oil crops such as soybean and Semen Brassicae campestris, oil palm and Chinese pistache, the food and drink wet goods that gives up, and is fine petroleum diesel surrogate.But the biofuel 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 biofuel 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-propylene glycol and ethylene glycol among the patent US 5214219.This process using CuO/ZnO/Al
2O
3Be catalyzer, copper zinc atom ratio is 0.2～6, glycerol concentration 20～60%, and temperature of reaction is more than 200 ℃, pressure 5～20MPa, glycerol conversion yield is 93% o'clock, 1, the highly selective of 2-propylene glycol 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 reaction process higher.
Patent US 5616817 and CN 95121742.9 also adopt the liquid-phase hydrogenatin reaction process to produce 1 by glycerine, the 2-propylene glycol, employing contains the catalyzer of Co, Cu, Mn, Mo and mineral acid, glycerol concentration brings up to 86.5%, 210～220 ℃ of temperature of reaction, pressure 29.5MPa is under glycerine 100% transforms, 1, the highly selective of 2-propylene glycol reaches 95%.But this method hydrogen 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 pyruvic alcohol, and hydrogenation obtains 1 then, and the 2-propylene glycol is a catalyzer with the copper chromite, glycerol concentration 80 weight %, 200 ℃ of temperature of reaction, pressure 1～2MPa, glycerol conversion yield 46.6%, 1,2-propylene glycol selectivity 85%.Though reaction pressure reduces greatly, this method adopts two step still formula hydrogenation reaction technologies, and long flow path and product and catalyzer are not easily separated, and gathering of by product 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 temperature of reaction, pressure 1～3MPa, hydrogen and glycerine ratio 400: 1～600: 1, the residence time 0.3～1.5s.It is said,, can optionally produce 1,2-propylene glycol and propyl alcohol by adjusting catalyzer and processing parameter.Under glycerine 100% transforms, 1,2-propylene glycol 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 running 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 catalyzer and has been used for glycerine hydrogenation preparation 1, the method of 2-propylene glycol, but this method is not set forth the Preparation of catalysts method, and adopted less hydrogen and glycerine than (3: 1～15: 1), make temperature of reaction height, reaction heat not to remove fast, cause by product to increase, will shorten the work-ing life of catalyzer.
There are problems such as reaction pressure is big, running 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 catalyzer, has that material concentration height, hydrogen pressure are low, hydrogen and the glycerine mol ratio is moderate, temperature of reaction 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-propylene glycol.
Glycerine liquid-phase hydrogenatin preparation 1, the 2-propylene glycol is implemented by following technical solution:
Catalyst precursor is a kind of composite oxides, is to adopt coprecipitation method 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 method prepares the catalyzer precursor is: the copper source is cupric nitrate, neutralized verdigris or cupric chloride, and the zirconium source is zirconium oxychloride, zirconium nitrate or zirconium alkoxide, and the titanium source is titanium sulfate titanium tetrachloride or titan-alkoxide, and the tungsten source is an ammonium metawolframate, 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 violent stirring, 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 cupric nitrate, neutralized verdigris or cupric chloride, and the zirconium source is a zirconium white, and the titanium source is zirconium white (titanium dioxide or a rutile), and the tungsten source is a Tungsten oxide 99.999, and the molybdenum source is a molybdenum oxide.The process of immersion process for preparing catalyst precursor is: at first the zirconium white of metering and titanium oxide or Tungsten oxide 99.999 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 airflows.
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.Catalyzer through hydrogen reducing activation preparation is used to the glycerine hydrogenation reaction, hydrogenation reaction adopts trickle bed liquid-phase hydrogenatin technology, and reaction conditions is: glycerine weight percent concentration 20～100%, 150～300 ℃ of temperature of reaction, pressure 1～20MPa, liquid air speed are 0.2～4.0h
-1, hydrogen and glycerine mol ratio 2～400, preferred reaction conditions is: glycerine weight percent concentration 60～90%, 180～250 ℃ of temperature of reaction, 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, temperature of reaction 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.
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 cupric nitrate, 2.0g polyoxyethylene 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 catalyzer composition sees Table 1).
Catalyzed reaction adopts trickle-bed reactor, loaded catalyst 7.5g, and fill with quartz sand at two ends.Before catalyzer uses at 260 ℃, 2.0MPa and air speed 500h
-1Condition under logical hydrogen reducing handle 8h.Weight percent concentration is that 60% glycerine solution enters reactor and carries out hydrogenation reaction after 150 ℃ of preheatings, and reaction conditions is: hydrogen 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.Catalyst 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.Catalyst component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 12
With 14.7g zirconium white, 6.9g molybdenum oxide mixed grinding, obtain mixture at 550 ℃ of roasting 8h, flood the aqueous solution that 400ml contains the 15.2g cupric 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.
Catalyst component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 13
With 12.3g zirconium white, 9.3g Tungsten oxide 99.999 mixed grinding, obtain mixture at 600 ℃ of roasting 8h, flood the aqueous solution that 400ml contains the 15.2g cupric 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.
Catalyst 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 cupric nitrate, 2.0g polyoxyethylene 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.
Catalyst component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 15
39.8g zirconium oxychloride, 13.5g ammonium metawolframate, 15.2g cupric nitrate, 2.0g polyoxyethylene 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.
Catalyst component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 16-24
Preparation of Catalyst and reaction process are with embodiment 3, and difference is glycerine hydrogenation reaction conditions difference.Catalyst component sees Table 1, hydrogenation conditions and the results are shown in Table 2.
Embodiment 25
Catalyzer and reaction conditions are investigated its stability with embodiment 3.Catalyst 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 pickling process pickling 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 | Cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate cupric nitrate | Zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium oxychloride zirconium white oxidation zirconium 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 99.999 titanium sulfate ammonium metawolframate 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 conditions and the result of each embodiment of table 2
| Embodiment | Glycerol concentration (weight %) | Temperature of reaction (℃) | Reaction pressure (MPa) | H 2/ glycerine mol ratio | Air speed (h -1) | Transformation efficiency (%) | 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 catalyzer
| Reaction times (h) | Glycerol concentration (weight %) | Temperature of reaction (℃) | Reaction pressure (MPa) | H 2/ glycerine mol ratio | Air speed (h -1) | Transformation efficiency (%) | 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 (5)
1. glycerine hydrogenation preparation 1, the Application of Catalyst of 2-propylene glycol, it is characterized in that adopting this catalyst precursor of coprecipitation method or immersion process for preparing, this catalyst precursor is composite oxides, its nonoxygen element consists of Cu-Zr-A, wherein A is selected from a kind of in tungsten or the molybdenum, and the weight percent content that Cu accounts for catalyst precursor is 10～30%, and the A/Zr atomic ratio is 0.2～5.0; This catalyst precursor carries out reduction activation in 200～450 ℃ hydrogen gas stream, make to be used for glycerine hydrogenation preparation 1, the catalyzer of 2-propylene glycol; This catalyzer is used for glycerine hydrogenation preparation 1, and the reaction conditions of 2-propylene glycol is: the glycerine weight percent concentration is 20～100%, and the hydrogenation reaction temperature is 150～300 ℃, and pressure is 1～2MPa, and the liquid air speed is 0.2～4.0h
-1, hydrogen and glycerine mol ratio are 2～400.
2. according to the described Application of Catalyst of claim 1, it is characterized in that the raw material that coprecipitation method prepares this catalyst precursor is: the copper source is cupric nitrate, neutralized verdigris or cupric chloride, the zirconium source is zirconium oxychloride, zirconium nitrate or zirconium alkoxide, and the tungsten source is an ammonium metawolframate, and the molybdenum source is an ammonium paramolybdate; The process that coprecipitation method prepares this catalyst precursor is: at first copper source and the zirconium source compound with metering adds in the entry successively with the tungsten source or with the molybdenum source compound and mixes, add surfactant polyethylene or polyvinyl alcohol again, under 40-80 ℃ of violent stirring, 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 airflows in 120 ℃ of baking ovens.
3. according to the described Application of Catalyst of claim 1, it is characterized in that the raw material of this catalyst precursor of immersion process for preparing is: the copper source is cupric nitrate, neutralized verdigris or cupric oxide, and the zirconium source is a zirconium white, and the tungsten source is a Tungsten oxide 99.999, and the molybdenum source is a molybdenum oxide; The process of this catalyst precursor of immersion process for preparing is: at first zirconium white and Tungsten oxide 99.999 or the molybdenum oxide powder with metering mixes, the copper source aqueous solution that measures of dipping then, and after the drying, roasting obtains catalyst precursor in 350～600 ℃ of airflows.
4. according to the described Application of Catalyst of claim 1, it is characterized in that this catalyst precursor is used for glycerine hydrogenation preparation 1 by hydrogen reducing activation preparation, the catalyzer of 2-propylene glycol, the hydrogen reducing activation condition is: temperature 200-450 ℃, pressure 1.0～5.0MPa, hydrogen gas space velocity 100～1000h
-1, 1～10 hour recovery time.
5. Application of Catalyst according to claim 1, it is characterized in that this catalyzer is used for glycerine hydrogenation preparation 1, the reaction conditions of 2-propylene glycol is: the glycerine weight percent concentration is 60～90%, the hydrogenation reaction temperature is 180～250 ℃, pressure is 3.0～8.0MPa, and the liquid air speed is 0.4～2.0h
-1, hydrogen and glycerine mol ratio are 10～100.
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Cited By (1)
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|---|---|---|---|---|
| US9464015B2 (en) | 2013-03-07 | 2016-10-11 | University Of Saskatchewan | Process for hydrogenolysis of glycerol |
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| US8071820B2 (en) * | 2008-12-23 | 2011-12-06 | Uop Llc | Method for converting glycerol to propanol |
| 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 |
| CN102924233B (en) * | 2012-10-20 | 2015-04-15 | 青岛科技大学 | Method for preparing propylene glycol by glycerin hydrogenolysis |
| 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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| US9464015B2 (en) | 2013-03-07 | 2016-10-11 | University Of Saskatchewan | Process for hydrogenolysis of glycerol |
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