CN104557452B - Method for catalyzing glycerinum one-step hydrogenolysis reaction through nickel-based catalyst - Google Patents
Method for catalyzing glycerinum one-step hydrogenolysis reaction through nickel-based catalyst Download PDFInfo
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- CN104557452B CN104557452B CN201510000778.7A CN201510000778A CN104557452B CN 104557452 B CN104557452 B CN 104557452B CN 201510000778 A CN201510000778 A CN 201510000778A CN 104557452 B CN104557452 B CN 104557452B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
- B01J2523/80—Constitutive chemical elements of heterogeneous catalysts of Group VIII of the Periodic Table
- B01J2523/84—Metals of the iron group
- B01J2523/847—Nickel
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Abstract
The invention relates to a method for catalyzing glycerinum one-step hydrogenolysis reaction through a nickel-based catalyst. The nickel-based catalyst is a columnar tabletting nickel catalyst, the active component of the nickel-based catalyst is the non-noble metal nickel, the nickel content accounts for 10-50% of the total mass of the nickel-based catalyst, and a carrier of the nickel-based catalyst is gamma-Al2O3. Under the catalytic action of the nickel-based catalyst, the reaction temperature is 180-250 DEG C, the aqueous solution concentration of glycerinum is 10-80%, the reaction pressure is 0.5-6 Mpa, the airspeed of feed liquid is 0.1-1/h, the filling height of the catalyst is 40 cm, and the glycerinum is decomposed into 1,2-propylene glycol in a highly selective manner.
Description
Technical field
The present invention relates to a kind of method of utilization nickel-base catalyst catalyzing glycerol one step hydrogenolysis, specifically a kind of post
Shape granule nickel-base catalyst preparation and its prepare the application in 1,2- propylene glycol in one-step glycerol hydrogenolysis.
Technical background
With the increasingly exhaustion of fossil energy, biodiesel is developed rapidly as a kind of new regenerative resource,
But often produce 9 kilograms of biodiesel and just have about 1 kilogram of crude glycerol by-product to produce, how to effectively utilize by-product glycerin
Become the hot issue of current research.
Glycerol can be efficiently solved above-mentioned by the chemicals that high temperature hydrogenolysis is converted into other high added values such as propylene glycol
Problem.Propylene glycol is a kind of important industrial chemicals, has the features such as nontoxic, low boiling and good polymerization, extensively
For producing unsaturated polyester (UP), polyurethane resin etc., widely should also have in the industries such as food, cosmetics, medicine
With.
At present, glycerine hydrogenation is prepared propylene glycol and is primarily present problems with：1. use noble metal catalyst, increase throwing
Money cost, so as to economic performance is poor, lacks the market competitiveness.2. in catalyst, contain the gold of the environment that is detrimental to health, pollutes
Belong to element.3. poor catalyst stability, short life.4. High Temperature High Pressure, higher to equipment requirements, increase equipment investment
This.5. the solvent of dissolving glycerol is reagent, increases Productive statistics cost.6. use tank reactor, solid-liquid is not readily separated,
The reaction contact with long-lasting catalytic for the feed liquid is easily caused by-product and generates, and reduces the selectivity of product, and affects catalyst
Service life.7. deliberately pursue the conversion ratio of glycerol, and have ignored the selectivity of target product.
Patent CN102424648B authorizes a kind of method of preparing 1,2-propylene glycol by catalytic hydrogenolysis of glycerin, and this method adopts kettle
Formula is reacted, and solid-liquid is not readily separated, and the reaction contact with long-lasting catalytic for the feed liquid is easily caused by-product and generates, and affects catalyst
Service life, and this method response time is oversize, increased production cost.Patent CN12557872A discloses a kind of glycerol one
The method that step hydrogenolysis prepares propylene glycol, this method adopts ethanol as solvent, and the response time is also relatively long, and production cost is relatively
High.Patent CN102731257A discloses a kind of method that selectivity containing sugar compounds prepares propylene glycol, this method reaction pressure phase
To higher, higher to equipment requirements, operating procedure is more complicated.CN102924233A discloses a kind of hydrogenolysis of glycerin and prepares propylene glycol
Method, this method selects fixed bed reactors as reaction unit, and operation simply can continuously produce, but used catalyst
It is with coprecipitation preparation, belong to loaded catalyst, thus while catalytic efficiency is higher, but active component is more easy to fall off, from
And affect the service life of catalyst.CN103524302A discloses the technique side that a kind of glycerine hydrogenation prepares 1,3- propylene glycol
Method, reaction desirable pressure is relatively low, but the response time is relatively long, and catalyst employs noble metal catalyst, increased
Production cost.
Content of the invention
For above-mentioned prior art problem, the invention provides a kind of anti-using nickel-base catalyst catalyzing glycerol one step hydrogenolysis
The method answered, in the presence of this catalyst, glycerol can efficient hydrogenolysis.
For achieving the above object, the technical scheme that the present invention takes is：
A kind of method of utilization nickel-base catalyst catalyzing glycerol one step hydrogenolysis, wherein said nickel-base catalyst is column
Wafers Raney nickel, active component is base metal nickel, and the content of nickel is the 10 ~ 50% of catalyst gross mass, and carrier is
γ-Al2O3；
The preparation method of described nickel-base catalyst is：The nickel nitrate aqueous solution of 0.5mol/L ~ 3mol/L and ammonia are pressed mole
Ratio 1:1~1:4 reactions form NiOH precipitation, then filtered, dry, and take the NiOH after drying to add γ-Al2O3Powder, two
Person's mass ratio is 1:1~1:10, add the porogen accounting for gross mass 1% ~ 10%, after mix homogeneously, compression molding；By its high temperature
Roasting Decomposition, sintering temperature finally carries out prereduction, hydrogen with hydrogen to NiO for 300 ~ 800 DEG C so that NiOH is decomposed into NiO
Pressure is 0.1 ~ 0.2Mpa, and tail gas flow velocity is 5 ~ 10mL/min, and heating rate is 20 ~ 40 DEG C/h, and maximum temperature is 150 ~ 250
DEG C, total recovery time is 5 ~ 25h, obtains cylindrical particle nickel-base catalyst after reduction；
In the presence of above-mentioned nickel-base catalyst, the aqueous solution hydrocracking of glycerol in reaction unit generates 1,2- the third two
Alcohol, the concentration of glycerine water solution is 10 ~ 80%；Reaction temperature is 180 ~ 250 DEG C, and reaction Hydrogen Vapor Pressure is 0.5 ~ 6Mpa, and feed liquid is empty
Speed is 0.1 ~ 1h-1, in reaction unit, the packed height of catalyst is 20 ~ 50cm.
Further, described porogen includes：Nitric acid, ethanol, deionized water, methanol, toluene, Pulvis Talci, wood powder, urine
Element, polyurethane（PU）, Polyvinylpyrrolidone（PVP）, one of PEG4000 or more than one.
Further, the concentration of described nickel nitrate aqueous solution is preferably 1 ~ 3mol/L, nickel nitrate aqueous solution and ammonia massage
That ratio preferably 1:1~1:2, described nickel hydroxide and γ-Al2O3The mass ratio of powder is preferably 1:1~1:5, described porogen
Quality is preferably the 1% ~ 5% of gross mass.Described sintering temperature is preferably 450 ~ 650 DEG C, and the maximum temperature in pre-reduction is excellent
Elect 180 ~ 220 DEG C as, total recovery time is preferably 10 ~ 20h.
Further, described reaction unit is drip bed reaction device, and the mass concentration of described glycerine water solution is relatively
Good be worth for 20% ~ 60%, optimum is 20% ~ 50%；The preferred values of hydrocracking reaction temperature is 200 ~ 220 DEG C, reactive hydrogen air pressure
The preferred values of power is 4 ~ 5Mpa, and the preferred values of reaction velocity is 0.1 ~ 0.3h-1.
Further, described beds packed height is 40cm.
Using cylindrical particle Raney nickel of the present invention, on trickle bed, continuous hydrogenolysis preparation 1,2- propylene glycol has
Following advantage：
1) present invention adopts Non oil-based route, can effectively alleviate fossil energy crisis.
2), not using noble metal catalyst, Financial cost is relatively low for catalyst preparation process.
3) catalytic performance of catalyst is good, and treating capacity is big and catalyst energy recycled is more than half a year.
4) this technique does not produce three-waste pollution, reaches zero-emission, is a kind of sustainable development route of green.
5) adopt trickle bed reactor, operating procedure is simple, can continuously be produced greatly.
6) target product selectivity is good, and product quality is high.
Specific embodiment
The present invention will be illustrated in greater detail by embodiment below, and these embodiments will be not intended to be limited to the guarantor of the present invention
Shield scope.
Embodiment 1：
First nickel nitrate is dissolved in the solution that water is configured to 3mol/L, then by it in molar ratio 1 with ammonia:1.5 reaction shapes
Become NiOH precipitation, then filtered, dry for standby.The nickel hydroxide after drying is taken to add γ-Al2O3Powder, mass ratio is 1:
1, will both mix homogeneously, add methanol, mass ratio is the 1% of gross mass, all substances stirred kneading so as to mix homogeneously
Carry out compression molding again.Then carry out high-temperature roasting, so that NiOH is decomposed, sintering temperature is 650 DEG C.Finally by the catalysis after roasting
Agent carries out hydrogen reducing, and Hydrogen Vapor Pressure is 0.2Mpa, and tail gas flow velocity is 10mL/min, temperature programming, and heating rate is 40 DEG C/h,
Reduction temperature is 220 DEG C, when temperature rises to 100 DEG C of insulation 4h, 180 DEG C of insulation 4h, is incubated 2h, total recovery time is about when 220 DEG C
15h.After prereduction terminates, stop heating, maintain the hydrogen of reaction system to be pressed in 0.2 more than MPa, catalyst preserves stand-by；Or treat
Reaction tube temperature close to room temperature when injection deionized water sealing preserve stand-by.
Adding the catalyst of above-mentioned preparation to make the bed packed height of catalyst in trickle bed reactor is 40cm, opens
Hydrogen gas cylinder displaced air 6 times, reacting by heating device, control 200 DEG C of temperature, be passed through hydrogen and put tail gas, Hydrogen Vapor Pressure is
4Mpa, in the glycerine water solution injected system being 50% by concentration with constant flow pump, volume space velocity is 0.1h-1, question response feed liquid reaches
Air speed volume samples after reacting 30min, and carries out quantitative analyses with GC.The conversion per pass of glycerol is 83%, product 1,2 third
The selectivity of glycol is 89%.
Embodiment 2：
First nickel nitrate is dissolved in the solution that water is configured to 2mol/L, then by it in molar ratio 1 with ammonia:1 reaction is formed
NiOH precipitates, and is then filtered, dry for standby.The nickel hydroxide after drying is taken to add γ-Al2O3Powder, mass ratio is 1:5,
Will both mix homogeneously, add methanol, mass ratio is the 5% of gross mass, all substances are stirred kneading so as to mix homogeneously again
Carry out compression molding.Then carry out high-temperature roasting, so that NiOH is decomposed, sintering temperature is 450 DEG C.Finally by the catalyst after roasting
Carry out hydrogen reducing, Hydrogen Vapor Pressure is 0.1Mpa, tail gas flow velocity is 5mL/min, temperature programming, heating rate is 20 DEG C/h, also
Former temperature is 180 DEG C, when temperature rises to 100 DEG C of insulation 1h, 180 DEG C of insulations 1h, about 10h of total recovery time.After prereduction terminates,
Stop heating, maintain the hydrogen of reaction system to be pressed in 0.2 more than MPa, catalyst preserves stand-by；Or question response pipe temperature is close to room
When warm, injection deionized water sealing preserve is stand-by.
Adding the catalyst of above-mentioned preparation to make the bed packed height of catalyst in trickle bed reactor is 30cm, opens
Hydrogen gas cylinder displaced air 6 times, reacting by heating device, control 210 DEG C of temperature, be passed through hydrogen and put tail gas, Hydrogen Vapor Pressure is
4.5Mpa, in the glycerine water solution injected system being 30% by concentration with constant flow pump, volume space velocity is 0.2h-1, question response feed liquid reaches
React sampling after 30min to air speed volume, and carry out quantitative analyses with GC.The conversion per pass of glycerol is 88%, product 1,2
The selectivity of propylene glycol is 92%.
Embodiment 3：
First nickel nitrate is dissolved in the solution that water is configured to 1mol/L, then by it in molar ratio 1 with ammonia:2 reactions are formed
NiOH precipitates, and is then filtered, dry for standby.The nickel hydroxide after drying is taken to add γ-Al2O3Powder, mass ratio is 1:
2.5, both mix homogeneously add methanol, mass ratio is the 2.5% of gross mass, all substances are stirred kneading so as to mix
Uniformly carry out compression molding again.Then carry out high-temperature roasting, so that NiOH is decomposed, sintering temperature is 500 DEG C.Finally by after roasting
Catalyst carries out hydrogen reducing, and Hydrogen Vapor Pressure is 0.15Mpa, and tail gas flow velocity is 7mL/min, temperature programming, and heating rate is 30
DEG C/h, reduction temperature be 200 DEG C, when temperature rise to 100 DEG C insulation 4h, 180 DEG C insulation 4h, when 200 DEG C be incubated 1h, always reduce when
Between about 20h.After prereduction terminates, stop heating, maintain the hydrogen of reaction system to be pressed in 0.2 more than MPa, catalyst preserves stand-by；
Or injection deionized water sealing preserve is stand-by during question response pipe temperature near room temperature.
Adding the catalyst of above-mentioned preparation to make the bed packed height of catalyst in trickle bed reactor is 35cm, opens
Hydrogen gas cylinder displaced air 6 times, reacting by heating device, control 220 DEG C of temperature, be passed through hydrogen and put tail gas, Hydrogen Vapor Pressure is
5Mpa, in the glycerine water solution injected system being 20% by concentration with constant flow pump, volume space velocity is 0.3h-1, question response feed liquid reaches
Air speed volume samples after reacting 30min, and carries out quantitative analyses with GC.The conversion per pass of glycerol is 97%, product 1,2 third
The selectivity of glycol is 77%.
Embodiment 4 ~ 8
Control material liquid glycerol is same concentration, and feed volume air speed is same value, implements to require to press embodiment 1, table 1
For the impact to preparing 1,2-dihydroxypropane by glycerine hydrogenation for the concrete reaction condition temperature and pressure, the conversion per pass of glycerol and product
The selectivity of thing 1,2- propylene glycol is as follows.
Table 1 reaction temperature and pressure prepare the impact of 1,2 propylene glycol to glycerine hydrogenation
Embodiment 9 ~ 13
Control material liquid glycerol is same concentration, and reaction condition temperature and pressure keeps indefinite for determination value, and implementing will
Ask by embodiment 1, table 2 is that concrete reaction condition feed volume air speed prepares the impact of 1,2 propylene glycol to glycerine hydrogenation, glycerol
The selectivity of conversion per pass and product 1,2 propylene glycol is as follows.
Table 2 feed volume air speed prepares the impact of 1,2 propylene glycol to glycerine hydrogenation
| Embodiment | Volume space velocity（h-1） | Glycerol conversion per pass（%） | 1,2 propylene glycol selectivitys（%） |
| 9 | 0.18 | 98 | 89 |
| 10 | 0.26 | 89 | 91 |
| 11 | 0.31 | 84 | 93 |
| 12 | 0.36 | 78 | 93 |
| 13 | 0.45 | 71 | 97 |
Embodiment 14 ~ 18
Control reaction condition temperature and pressure and glycerine feed volume space velocity to keep indefinite for determination value, implement requirement and press
Embodiment 1, table 3 is that concrete reaction condition glycerine feed concentration prepares the impact of 1,2 propylene glycol, the one way of glycerol to glycerine hydrogenation
The selectivity of conversion ratio and product 1,2 propylene glycol is as follows.
Table 3 glycerine feed concentration prepares the impact of 1,2 propylene glycol to glycerine hydrogenation
| Embodiment | The concentration of glycerol（wt%） | Glycerol conversion per pass（%） | 1,2 propylene glycol selectivitys（%） |
| 14 | 20 | 98 | 75 |
| 15 | 50 | 87 | 90 |
| 16 | 55 | 82 | 94 |
| 17 | 58 | 78 | 95 |
| 18 | 62 | 74 | 96 |
Claims (5)
1. a kind of method of utilization nickel-base catalyst catalyzing glycerol one step hydrogenolysis it is characterised in that：
Described nickel-base catalyst is column wafers Raney nickel, and active component is base metal nickel, and the content of nickel is catalysis
The 10 ~ 50% of agent gross mass, carrier is γ-Al2O3；
The preparation method of described nickel-base catalyst is：The nickel nitrate aqueous solution of 0.5mol/L ~ 3mol/L and ammonia in molar ratio 1:1
~1:4 reactions form NiOH precipitation, then filtered, dry, and take the NiOH after drying to add γ-Al2O3Powder, both quality
Than for 1:1~1:10, add the porogen accounting for gross mass 1% ~ 10%, after mix homogeneously, compression molding；Its high-temperature roasting is divided
Solution, sintering temperature finally carries out prereduction with hydrogen to NiO, Hydrogen Vapor Pressure is for 300 ~ 800 DEG C so that NiOH is decomposed into NiO
0.1 ~ 0.2Mpa, tail gas flow velocity is 5 ~ 10mL/min, and heating rate is 20 ~ 40 DEG C/h, and maximum temperature is 150 ~ 250 DEG C, always also
The former time is 5 ~ 25h, obtains cylindrical particle nickel-base catalyst after reduction；
In the presence of above-mentioned nickel-base catalyst, the aqueous solution hydrocracking of glycerol in reaction unit generates 1,2-PD,
The mass concentration of glycerine water solution is 10 ~ 80%；Reaction temperature is 180 ~ 250 DEG C, and reaction Hydrogen Vapor Pressure is 0.5 ~ 6Mpa, feed liquid
Air speed is 0.1 ~ 1h-1, in reaction unit, the packed height of catalyst is 20 ~ 50cm；
Described porogen is methanol；
Described reaction unit is drip bed reaction device.
2. method according to claim 1 it is characterised in that：The concentration of described nickel nitrate aqueous solution is 1 ~ 3mol/L, nitre
Sour nickel aqueous solution and ammonia in molar ratio 1:1~1:2, described nickel hydroxide and γ-Al2O3The mass ratio of powder is 1:1~1:5, institute
The quality stating porogen is the 1% ~ 5% of gross mass.
3. method according to claim 1 it is characterised in that：Described sintering temperature is 450 ~ 650 DEG C, in pre-reduction
Maximum temperature be 180 ~ 220 DEG C, total recovery time be 10 ~ 20h.
4. method according to claim 1 it is characterised in that：The mass concentration of described glycerine water solution is 20% ~ 50%, plus
The temperature of hydrogen cracking reaction is 200 ~ 220 DEG C, and reaction Hydrogen Vapor Pressure is 4 ~ 5Mpa, and reaction velocity is 0.1 ~ 0.3h-1.
5. method according to claim 1 it is characterised in that：Described beds packed height is 40cm.
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| CN201510000778.7A CN104557452B (en) | 2015-01-04 | 2015-01-04 | Method for catalyzing glycerinum one-step hydrogenolysis reaction through nickel-based catalyst |
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| CN201510000778.7A CN104557452B (en) | 2015-01-04 | 2015-01-04 | Method for catalyzing glycerinum one-step hydrogenolysis reaction through nickel-based catalyst |
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| DE4442124A1 (en) * | 1994-11-26 | 1996-05-30 | Basf Ag | Process for the preparation of 1,2-propanediol |
| US7663004B2 (en) * | 2002-04-22 | 2010-02-16 | The Curators Of The University Of Missouri | Method of producing lower alcohols from glycerol |
| GB0614823D0 (en) * | 2006-07-26 | 2006-09-06 | Davy Process Techn Ltd | Process |
| CN101372444B (en) * | 2007-08-24 | 2011-04-20 | 中国科学院大连化学物理研究所 | Method for hydrocracking glycyl alcohol |
| JP5599193B2 (en) * | 2010-01-29 | 2014-10-01 | 国立大学法人 筑波大学 | Method for producing glycol |
| CN102091624B (en) * | 2010-12-01 | 2013-06-19 | 厦门大学 | Catalyst for preparing dihydric alcohol through hydrogenolysis of polyatomic alcohol and preparation method thereof |
| JP2014507270A (en) * | 2011-01-24 | 2014-03-27 | ビーエーエスエフ ソシエタス・ヨーロピア | Hydrogenation catalyst containing nickel-supported carbon |
| JP5654399B2 (en) * | 2011-03-28 | 2015-01-14 | 株式会社ダイセル | Process for producing hydrolyzate of glycerin |
| US8222462B2 (en) * | 2011-07-28 | 2012-07-17 | Uop Llc | Process for generation of polyols from saccharides |
| US8975453B2 (en) * | 2012-03-13 | 2015-03-10 | University Of Idaho | Catalytic conversion of glycerol or acetol to alcohols |
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