CN104557452A - Method for catalyzing one-step hydrogenolysis reaction of glycerol by using nickel-based catalyst - Google Patents
Method for catalyzing one-step hydrogenolysis reaction of glycerol by using nickel-based catalyst Download PDFInfo
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000007327 hydrogenolysis reaction Methods 0.000 title claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 235000011187 glycerol Nutrition 0.000 claims description 44
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 235000012431 wafers Nutrition 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 abstract description 51
- 229960004063 propylene glycol Drugs 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 239000000047 product Substances 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 6
- 230000004044 response Effects 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- 239000002551 biofuel Substances 0.000 description 2
- 230000005923 long-lasting effect Effects 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- NJTGANWAUPEOAX-UHFFFAOYSA-N molport-023-220-454 Chemical compound OCC(O)CO.OCC(O)CO NJTGANWAUPEOAX-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for catalyzing one-step hydrogenolysis reaction of glycerol by using a nickel-based catalyst. The catalyst is a columnar pressed nickel catalyst, the active component is non-noble metal nickel, the content of the nickel accounts for 10-50% of the total mass of the catalyst, and the carrier is gamma-Al2O3. Under the catalytic action of a nickel-based catalyst, the reaction temperature is 180-250 ℃, the concentration of the glycerol aqueous solution is 10-80%, the reaction pressure is 0.5-6 Mpa, and the space velocity of the feed liquid is 0.1-1 h-1The filling height of the catalyst is 40cm, and the glycerol is cracked into the 1, 2-propylene glycol with high selectivity.
Description
Technical field
The present invention relates to a kind of method utilizing nickel-base catalyst catalyzing glycerol one step hydrogenolysis, is a kind of preparation of cylindrical particle nickel-base catalyst and the application prepared in one-step glycerol hydrogenolysis in 1,2-PD thereof specifically.
Technical background
Along with the exhaustion day by day of fossil energy, biofuel is developed rapidly as a kind of novel renewable energy source, but often produce 9 kilograms of biofuel, 1 kilogram of crude glycerol by product of just having an appointment and produce, how to effectively utilize the hot issue that by-product glycerin becomes research at present.
The chemical that glycerine is converted into other high added values such as propylene glycol by high temperature hydrogenolysis can be solved the problem effectively.Propylene glycol is a kind of important industrial chemicals, has the features such as nontoxic, lower boiling and good polymerization, is widely used in and produces unsaturated polyester, urethane resin etc., be also widely used in the industries such as food, makeup, medicine.
At present, glycerine hydrogenation is prepared propylene glycol and mainly be there is following problem: 1. use noble metal catalyst, increase cost of investment, make its economic performance poor, lacks the market competitiveness.2. in catalyzer containing being detrimental to health, the metallic element of contaminate environment.3. poor catalyst stability, the life-span is short.4. High Temperature High Pressure, higher to equipment requirements, increase equipment investment cost.5. the solvent dissolving glycerine is reagent, increases Productive statistics cost.6. use tank reactor, solid-liquid is not easily separated, and the contact of reaction feed liquid and long-lasting catalytic easily causes by product to generate, and reduces the selectivity of product, and affects the work-ing life of catalyzer.7. deliberately pursue the transformation efficiency of glycerine, and have ignored the selectivity of target product.
Patent CN102424648B authorizes a kind of catalytic hydrogenolysis glycerine and prepares 1, the method of 2-propylene glycol, this method adopts still reaction, solid-liquid is not easily separated, the contact of reaction feed liquid and long-lasting catalytic easily causes by product to generate, affect the work-ing life of catalyzer, and this method reaction times is oversize, adds production cost.Patent CN12557872A discloses a kind of method of preparing propanediol through one-step glycerol hydrogenolysis, and this method adopts ethanol as solvent, and the reaction times is also relatively long, and production cost is relatively high.Patent CN102731257A discloses a kind of method that sugary compound selective prepares propylene glycol, and this method reaction pressure is relatively high, and higher to equipment requirements, operating procedure is more complicated.CN102924233A discloses a kind of method that hydrogenolysis of glycerin prepares propylene glycol, this method selects fixed-bed reactor as reaction unit, operation simply can continuous seepage, but used catalyst prepares by coprecipitation method, belong to loaded catalyst, although therefore catalytic efficiency is higher, active ingredient more easily comes off, thus affects the work-ing life of catalyzer.CN103524302A discloses the processing method that a kind of glycerine hydrogenation prepares 1,3-PD, and the required pressure of reaction is relatively low, but the reaction times is relatively long, and catalyzer have employed noble metal catalyst, adds production cost.
Summary of the invention
For above-mentioned prior art problem, the invention provides a kind of method utilizing nickel-base catalyst catalyzing glycerol one step hydrogenolysis, under the effect of this catalyzer, glycerine can efficient hydrogenolysis.
For achieving the above object, the technical scheme that the present invention takes is:
Utilize a method for nickel-base catalyst catalyzing glycerol one step hydrogenolysis, wherein said nickel-base catalyst is column wafers nickel catalyzator, and active ingredient is base metal nickel, and the content of nickel is 10 ~ 50% of catalyzer total mass, and carrier is γ-Al
2o
3;
The preparation method of described nickel-base catalyst is: the 1:1 ~ 1:4 reaction in molar ratio of the nickel nitrate aqueous solution of 0.5mol/L ~ 3mol/L and ammoniacal liquor forms NiOH precipitation, is then filtered, dries, get the NiOH after oven dry and add γ-Al
2o
3powder, both mass ratioes are 1:1 ~ 1:10, then add the pore-creating agent accounting for total mass 1% ~ 10%, after mixing, compression molding; Its high-temperature roasting is decomposed, maturing temperature is 300 ~ 800 DEG C, NiOH is made to be decomposed into NiO, finally carry out prereduction with hydrogen to NiO, hydrogen pressure is 0.1 ~ 0.2Mpa, and tail gas flow velocity is 5 ~ 10mL/min, temperature rise rate is 20 ~ 40 DEG C/h, top temperature is 150 ~ 250 DEG C, and total recovery time is 5 ~ 25h, obtains cylindrical particle nickel-base catalyst after reduction;
Under the effect of above-mentioned nickel-base catalyst, in reaction unit, the aqueous solution hydrocracking of glycerine generates 1,2-PD, and the concentration of aqueous glycerin solution is 10 ~ 80%; Temperature of reaction is 180 ~ 250 DEG C, and reactive hydrogen atmospheric pressure is 0.5 ~ 6Mpa, and feed liquid air speed is 0.1 ~ 1h
-1, in reaction unit, the packing height of catalyzer is 20 ~ 50cm.
Further, described pore-creating agent comprises: one or more in nitric acid, ethanol, deionized water, methyl alcohol, toluene, talcum powder, wood powder, urea, urethane (PU), polyvinylpyrrolidone (PVP), PEG4000.
Further, the concentration of described nickel nitrate aqueous solution is preferably 1 ~ 3mol/L, and nickel nitrate aqueous solution and ammoniacal liquor are preferably 1:1 ~ 1:2 in molar ratio, described nickel hydroxide and γ-Al
2o
3the mass ratio of powder is preferably 1:1 ~ 1:5, and the quality optimization of described pore-creating agent is 1% ~ 5% of total mass.Described maturing temperature is preferably 450 ~ 650 DEG C, and the top temperature in pre-reduction is preferably 180 ~ 220 DEG C, and total recovery time is preferably 10 ~ 20h.
Further, described reaction unit is trickle bed reaction unit, and the preferred values of the mass concentration of described aqueous glycerin solution is 20% ~ 60%, and optimum value is 20% ~ 50%; The preferred values of hydrocracking temperature of reaction is 200 ~ 220 DEG C, and the preferred values of reactive hydrogen atmospheric pressure is 4 ~ 5Mpa, and the preferred values of reaction velocity is 0.1 ~ 0.3h
-1.
Further, described beds packing height is 40cm.
Utilize cylindrical particle nickel catalyzator of the present invention continuous hydrogenolysis on trickle bed to prepare 1,2-PD tool to have the following advantages:
1) the present invention adopts Non oil-based route, can effectively alleviate fossil energy crisis.
2) catalyst preparation process does not use noble metal catalyst, and Financial cost is relatively low.
3) catalytic performance of catalyzer is good, more than treatment capacity large and catalyzer energy recycled half a year.
4) this technique does not produce three-waste pollution, reaches zero release, is a kind of Sustainable development route of green.
5) adopt trickle-bed reactor, operating procedure is simple, can carry out continuously large production.
6) target product selectivity is good, and quality product is high.
Embodiment
To illustrate in greater detail the present invention by embodiment below, and these embodiments do not attempt to limit the scope of the invention.
Embodiment 1:
First by water-soluble for the nickelous nitrate solution being mixed with 3mol/L, then by itself and ammoniacal liquor in molar ratio 1:1.5 react and form NiOH and precipitate, then filtered, dry for standby.Get the nickel hydroxide after oven dry and add γ-Al
2o
3powder, mass ratio is 1:1, both is mixed, and adds methyl alcohol, and mass ratio is 1% of total mass, and all substances are stirred kneading, makes it mix and carries out compression molding again.Then carry out high-temperature roasting, NiOH is decomposed, maturing temperature is 650 DEG C.Finally the catalyzer after roasting is carried out hydrogen reducing, hydrogen pressure is 0.2Mpa, and tail gas flow velocity is 10mL/min, temperature programming, temperature rise rate is 40 DEG C/h, and reduction temperature is 220 DEG C, when temperature rises to 100 DEG C of insulation 4h, 180 DEG C of insulation 4h, be incubated 2h when 220 DEG C, total recovery time is about 15h.After prereduction terminates, stop heating, maintain the hydrogen pressure of reaction system at 0.2 more than MPa, catalyzer is preserved stand-by; Or the sealing of injection deionized water is preserved stand-by during question response pipe temperature near room temperature.
The catalyzer adding above-mentioned preparation in trickle-bed reactor makes the bed packing height of catalyzer be 40cm, open hydrogen gas cylinder displaced air 6 times, reacting by heating device, control temperature 200 DEG C, pass into hydrogen and put tail gas, hydrogen pressure is 4Mpa, is that in the aqueous glycerin solution injected system of 50%, volume space velocity is 0.1h with constant flow pump by concentration
-1, question response feed liquid reaches after namely air speed volume reacts 30min and samples, and carries out quantitative analysis with GC.The per pass conversion of glycerine is 83%, product 1, and the selectivity of 2 propylene glycol is 89%.
Embodiment 2:
First by water-soluble for the nickelous nitrate solution being mixed with 2mol/L, then by itself and ammoniacal liquor in molar ratio 1:1 react and form NiOH and precipitate, then filtered, dry for standby.Get the nickel hydroxide after oven dry and add γ-Al
2o
3powder, mass ratio is 1:5, both is mixed, and adds methyl alcohol, and mass ratio is 5% of total mass, and all substances are stirred kneading, makes it mix and carries out compression molding again.Then carry out high-temperature roasting, NiOH is decomposed, maturing temperature is 450 DEG C.Finally the catalyzer after roasting is carried out hydrogen reducing, hydrogen pressure is 0.1Mpa, and tail gas flow velocity is 5mL/min, temperature programming, temperature rise rate is 20 DEG C/h, and reduction temperature is 180 DEG C, when temperature rises to 100 DEG C of insulation 1h, 180 DEG C of insulation 1h, total recovery time is about 10h.After prereduction terminates, stop heating, maintain the hydrogen pressure of reaction system at 0.2 more than MPa, catalyzer is preserved stand-by; Or the sealing of injection deionized water is preserved stand-by during question response pipe temperature near room temperature.
The catalyzer adding above-mentioned preparation in trickle-bed reactor makes the bed packing height of catalyzer be 30cm, open hydrogen gas cylinder displaced air 6 times, reacting by heating device, control temperature 210 DEG C, pass into hydrogen and put tail gas, hydrogen pressure is 4.5Mpa, is that in the aqueous glycerin solution injected system of 30%, volume space velocity is 0.2h with constant flow pump by concentration
-1, question response feed liquid reaches after namely air speed volume reacts 30min and samples, and carries out quantitative analysis with GC.The per pass conversion of glycerine is 88%, product 1, and the selectivity of 2 propylene glycol is 92%.
Embodiment 3:
First by water-soluble for the nickelous nitrate solution being mixed with 1mol/L, then by itself and ammoniacal liquor in molar ratio 1:2 react and form NiOH and precipitate, then filtered, dry for standby.Get the nickel hydroxide after oven dry and add γ-Al
2o
3powder, mass ratio is 1:2.5, both is mixed, and adds methyl alcohol, and mass ratio is 2.5% of total mass, and all substances are stirred kneading, makes it mix and carries out compression molding again.Then carry out high-temperature roasting, NiOH is decomposed, maturing temperature is 500 DEG C.Finally the catalyzer after roasting is carried out hydrogen reducing, hydrogen pressure is 0.15Mpa, and tail gas flow velocity is 7mL/min, temperature programming, temperature rise rate is 30 DEG C/h, and reduction temperature is 200 DEG C, when temperature rises to 100 DEG C of insulation 4h, 180 DEG C of insulation 4h, be incubated 1h when 200 DEG C, total recovery time is about 20h.After prereduction terminates, stop heating, maintain the hydrogen pressure of reaction system at 0.2 more than MPa, catalyzer is preserved stand-by; Or the sealing of injection deionized water is preserved stand-by during question response pipe temperature near room temperature.
The catalyzer adding above-mentioned preparation in trickle-bed reactor makes the bed packing height of catalyzer be 35cm, open hydrogen gas cylinder displaced air 6 times, reacting by heating device, control temperature 220 DEG C, pass into hydrogen and put tail gas, hydrogen pressure is 5Mpa, is that in the aqueous glycerin solution injected system of 20%, volume space velocity is 0.3h with constant flow pump by concentration
-1, question response feed liquid reaches after namely air speed volume reacts 30min and samples, and carries out quantitative analysis with GC.The per pass conversion of glycerine is 97%, product 1, and the selectivity of 2 propylene glycol is 77%.
Embodiment 4 ~ 8
Controlling stock liquid glycerine is same concentration, and feed volume air speed is same value, and urban d evelopment is by embodiment 1, table 1 prepares 1 for concrete reaction conditions temperature and pressure to glycerine hydrogenation, the impact of 2-propylene glycol, the per pass conversion of glycerine and the selectivity of product 1,2-PD as follows.
Table 1 temperature of reaction and pressure prepare 1 to glycerine hydrogenation, the impact of 2 propylene glycol
Embodiment 9 ~ 13
Controlling stock liquid glycerine is same concentration, and reaction conditions temperature and pressure is that determined value maintenance is indefinite, urban d evelopment is by embodiment 1, table 2 prepares 1 for concrete reaction conditions feed volume air speed to glycerine hydrogenation, the impact of 2 propylene glycol, the per pass conversion of glycerine and the selectivity of product 1,2 propylene glycol as follows.
Table 2 feed volume air speed prepares 1 to glycerine hydrogenation, the impact of 2 propylene glycol
| Embodiment | Volume space velocity (h -1） | Glycerine per pass conversion (%) | 1,2 propylene glycol selectivity (%) |
| 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 conditions temperature and pressure and glycerine feed volume space velocity are that determined value keeps indefinite, urban d evelopment is by embodiment 1, table 3 prepares 1 for concrete reaction conditions glycerine feed concentration to glycerine hydrogenation, the impact of 2 propylene glycol, the per pass conversion of glycerine and the selectivity of product 1,2 propylene glycol as follows.
Table 3 glycerine feed concentration prepares 1 to glycerine hydrogenation, the impact of 2 propylene glycol
| Embodiment | The concentration (wt%) of glycerine | Glycerine per pass conversion (%) | 1,2 propylene glycol selectivity (%) |
| 14 | 20 | 98 | 75 |
| 15 | 50 | 87 | 90 |
| 16 | 55 | 82 | 94 |
| 17 | 58 | 78 | 95 |
| 18 | 62 | 74 | 96 |
Claims (7)
1. utilize a method for nickel-base catalyst catalyzing glycerol one step hydrogenolysis, it is characterized in that:
Described nickel-base catalyst is column wafers nickel catalyzator, and active ingredient is base metal nickel, and the content of nickel is 10 ~ 50% of catalyzer total mass, and carrier is γ-Al
2o
3;
The preparation method of described nickel-base catalyst is: the 1:1 ~ 1:4 reaction in molar ratio of the nickel nitrate aqueous solution of 0.5mol/L ~ 3mol/L and ammoniacal liquor forms NiOH precipitation, is then filtered, dries, get the NiOH after oven dry and add γ-Al
2o
3powder, both mass ratioes are 1:1 ~ 1:10, then add the pore-creating agent accounting for total mass 1% ~ 10%, after mixing, compression molding; Its high-temperature roasting is decomposed, maturing temperature is 300 ~ 800 DEG C, NiOH is made to be decomposed into NiO, finally carry out prereduction with hydrogen to NiO, hydrogen pressure is 0.1 ~ 0.2Mpa, and tail gas flow velocity is 5 ~ 10mL/min, temperature rise rate is 20 ~ 40 DEG C/h, top temperature is 150 ~ 250 DEG C, and total recovery time is 5 ~ 25h, obtains cylindrical particle nickel-base catalyst after reduction;
Under the effect of above-mentioned nickel-base catalyst, in reaction unit, the aqueous solution hydrocracking of glycerine generates 1,2-PD, and the concentration of aqueous glycerin solution is 10 ~ 80%; Temperature of reaction is 180 ~ 250 DEG C, and reactive hydrogen atmospheric pressure is 0.5 ~ 6Mpa, and feed liquid air speed is 0.1 ~ 1h
-1, in reaction unit, the packing height of catalyzer is 20 ~ 50cm.
2. method according to claim 1, is characterized in that: described pore-creating agent comprises: one or more in nitric acid, ethanol, deionized water, methyl alcohol, toluene, talcum powder, wood powder, urea, urethane, polyvinylpyrrolidone, PEG4000.
3. method according to claim 1, is characterized in that: the concentration of described nickel nitrate aqueous solution is 1 ~ 3mol/L, nickel nitrate aqueous solution and ammoniacal liquor 1:1 ~ 1:2 in molar ratio, described nickel hydroxide and γ-Al
2o
3the mass ratio of powder is 1:1 ~ 1:5, and the quality of described pore-creating agent is 1% ~ 5% of total mass.
4. method according to claim 1, is characterized in that: described maturing temperature is 450 ~ 650 DEG C, and the top temperature in pre-reduction is 180 ~ 220 DEG C, and total recovery time is 10 ~ 20h.
5. method according to claim 1, is characterized in that: described reaction unit is trickle bed reaction unit.
6. method according to claim 1, is characterized in that: the mass concentration of described aqueous glycerin solution is 20% ~ 50%, and the temperature of hydrocracking reaction is 200 ~ 220 DEG C, and reactive hydrogen atmospheric pressure is 4 ~ 5Mpa, and reaction velocity is 0.1 ~ 0.3h
-1.
7. method according to claim 1, is characterized in that: described beds packing height is 40cm.
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|---|---|---|---|
| CN201510000778.7A CN104557452B (en) | 2015-01-04 | 2015-01-04 | Method for catalyzing one-step hydrogenolysis reaction of glycerol by using nickel-based catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112246245A (en) * | 2020-09-16 | 2021-01-22 | 华南理工大学 | Supported nickel-based catalyst and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN104557452B (en) | 2017-02-22 |
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