CN1810371A - Catalyst for hydrogenating 3-hydroxy propaldehyde to prepare 1, 3-propylene glycol - Google Patents
Catalyst for hydrogenating 3-hydroxy propaldehyde to prepare 1, 3-propylene glycol Download PDFInfo
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Abstract
The catalyst for hydrogenating 3-hydroxy propaldehyde to prepare 1, 3-propylene glycol is supported Ni-Mo-X/A catalyst with the molecular sieve, oxide or their mixture as carrier and Ni, Mo and one third metal as the active components. The catalyst is used in the hydrogenating water solution of 3-hydroxy propaldehyde to prepare 1, 3-propylene glycol, and has high activity, high selectivity, mild reaction condition and high stability.
Description
Technical field
The present invention relates to a kind of 3-3-hydroxyl propionaldehyde hydrogenation to produce and be equipped with 1, the catalyst of ammediol.
Background technology
3-hydroxy propanal hydrogenation is to synthesize 1, the important channel of ammediol.1, ammediol is a kind of important chemical material, is mainly used in the production polymer, and as poly terephthalic acid 1, ammediol ester (PTT), thermoplastic polyurethane etc. are on a small quantity as solvent, antifreeze and protective agent etc.The PTT molecule has Z type spring-like structures and unique physicochemical properties, thereby ptt fiber had both had good performances such as softness, easy coloring, have good resilience and antifouling property again, good prospects for application is arranged in fields such as carpet, engineering plastics, garment materials.The 3-hydroxy propanal can make by processes such as acrolein hydration, oxirane hydroformylations.Because the 3-hydroxy propanal is very unsettled material, multiple side reactions such as polymerization, condensation, decomposition take place in hydrogenation process easily, and these reaction meetings aggravate along with the rising of temperature, and the accessory substance that is generated can cause activity of such catalysts to reduce, and shortens the service life of catalyst.Therefore, select the catalyst of high activity, high selectivity, it is vital carrying out 3-hydroxy propanal hydrogenation reaction under alap reaction temperature.The 3-3-hydroxyl propionaldehyde hydrogenation to produce of having reported at present 1, the catalyst of ammediol are divided into Raney nickel type catalyst substantially, are the loaded catalyst of active component and are the catalyst three major types of main active component with nickel with platinum, palladium or ruthenium.
Use a kind of Raney nickel type catalyst of modifying with Cr, Zn, Mo, Fe or Cr+Fe to carry out 3-hydroxy propanal batch still formula hydrogenation system 1 among the patent CN1122568, ammediol, under the Hydrogen Vapor Pressure of 3.0～10.0MPa, earlier 50 ℃ of following hydrogenation reactions 60 minutes, then at 125～130 ℃ of following hydrogenation, can make 3-hydroxy propanal nearly 100% be converted into 1, ammediol.(0.02～0.08mm), reaction back separation difficulty is difficult to be applied in the large-scale industrial production but the particle diameter of this catalyst is less.Use the catalyst of a kind of active component among the patent CN1428322 as the Ni-A type, by the two-stage hydrogenation reaction 3-hydroxy propanal is converted into 1, ammediol, wherein A is any among Cr, Zn, Mo or the Fe in the catalyst, the mass content of A is 2.97～5.45%.Use the catalyst of the type, 3-hydroxy propanal nearly 100% is converted into 1, ammediol, but the less stable of catalyst.Adopt immersion process for preparing 3-hydroxy propanal hydrogenation catalyst among the patent CN1363544, with the aqueous solution that contains 5～50% nickel salts and 0.1～5% cobalt salt is maceration extract, with metal oxide, molecular sieve is carrier, through one or many dipping preparation catalyst, be 60 ℃, pressure 5.0MPa, air speed 9h in reaction temperature
-1The time, 3-hydroxy propanal conversion ratio 99.4%, 1, ammediol selectivity 99.1%.This patent only is described the Preparation of catalysts method, but the composition of catalyst do not define accurately, causes that this patent is difficult to be implemented.Use a kind of unsupported catalyst of mixing method preparation to carry out 3-3-hydroxyl propionaldehyde hydrogenation to produce 1 among the patent CN1145528, ammediol, catalyst contains 25～60% nickel, contains 5～20% molybdenums, 10～50% binding materials, wherein binding material is oxide species at least a of the oxide of silicon and silicate and zinc, aluminium, zirconium, magnesium and calcium, investigate with the reactivity that this catalyst has carried out 720 hours, the less stable of catalyst, and reactivity is not high.
Summary of the invention
The object of the present invention is to provide a kind of 3-3-hydroxyl propionaldehyde hydrogenation to produce to be equipped with 1, the good catalyst of ammediol, this catalyst is the loaded catalyst that contains Ni, Mo and the 3rd component, this catalyst is used for 3-hydroxy propanal aqueous solution hydrogenation preparing 1, ammediol when reaction, active, selectivity is high, the reaction condition gentleness, catalyst stability is good, thereby has solved the problem that prior art exists effectively.
The present invention is achieved by the following technical solutions:
A kind of 3-3-hydroxyl propionaldehyde hydrogenation to produce is equipped with 1, the Ni-Mo-X/A type loaded catalyst of ammediol, and wherein component X is any among Co, Mn, Cu, Cr, Ca, Zn, Fe, the W; Carrier A is molecular sieve ZSM-5, MCM-49, MCM-22, SAPO-11, SAPO-34, modenite, β zeolite, L zeolite branch, Y zeolite, overstable gamma zeolite or oxide γ-Al
2O
3, SiO
2, any in MgO or the amorphous aluminum silicate or their mixture, carrier A is preferably molecular sieve ZSM-5, MCM-49, SAPO-34, modenite, β zeolite, amorphous aluminum silicate, γ-Al
2O
3Or SiO
2In any or their mixture; The mass fraction of Ni is 9%～38% in the catalyst, is preferably 10%～25%; The mass fraction of component Mo is 7%～45%, is preferably 8%～20%; The mass fraction of component X is 1%～10%, is preferably 3%～8%.Catalyst needs to reduce in hydrogen before use, and reducing condition is Hydrogen Vapor Pressure 0.2～10.0MPa, hydrogen gas space velocity 200～1500h
-1, 300～500 ℃ of reduction temperatures, 2～20 hours recovery times, be preferably Hydrogen Vapor Pressure 2.0～8.0MPa, hydrogen gas space velocity 300～1000h
-1, 350～500 ℃ of reduction temperatures, 5～15 hours recovery times.Catalyst is infusion process or mixing method preparation.
It is presoma with support powder or fine grained and active component that mixing method prepares catalyst, mix and extrusion or compression molding by certain metering ratio as soluble-salt or metal oxide etc., and then dry, roasting becomes the metal oxide form.Pack into before catalyst uses and use hydrogen reducing in the reactor.
The immersion process for preparing catalyst be be mixed with the certain density soluble salts of active components aqueous solution according to certain metering than flooding in the catalyst carrier that adds moulding in advance, dry then, roasting becomes the metal oxide form.Pack into before catalyst uses and use hydrogen reducing in the reactor.
The specific embodiment
To be illustrated with specific embodiment below, but content of the present invention is not limited to these
Embodiment.Among each embodiment:
The 3-hydroxy propanal amount that conversion ratio %=reaction transforms/enter 3-hydroxy propanal amount * 100% of reactor
Selectivity %=1,3-hydroxy propanal amount * 100% that ammediol growing amount/reaction transforms
Embodiment 1～17
Mixing method prepares catalyst: with certain density nickel nitrate aqueous solution, MoO
3With the solubility salt aqueous solution of component X or the oxide of X,, mix and extrusion or compression molding than adding in the catalyst carrier according to certain metering, then 120 ℃ dry 20 hours down, 600 ℃ of following roastings 4 hours.Reduce to room temperature after roasting finishes, in the reactor of packing into, 450 ℃ with hydrogen reducing 4 hours, is adjusted to the required condition of reaction after reduction finishes.The composition of catalyst among each embodiment, the starting material kind of component X sees Table 1.
The Ni-Mo-X/A loaded catalyst of table 1 mixing method preparation is formed
| Embodiment | Component X | The starting material of component X | Carrier A | Ni content, % (quality) | Mo content, % (quality) | X content, % (quality) |
| Embodiment 1 | Co | Cobalt nitrate | γ-Al 2O 3 | 22 | 12 | 2.5 |
| Embodiment 2 | Mn | Manganese nitrate | SiO 2 | 21 | 15 | 3.5 |
| Embodiment 3 | Cu | Copper nitrate | Amorphous silicon aluminium | 20 | 11 | 3 |
| Embodiment 4 | Cr | Chromic nitrate | The HZSM-5 zeolite | 22 | 14 | 5 |
| Embodiment 5 | Cr | Chromium oxide | The SAPO-11 zeolite | 22 | 15 | 6.8 |
| Embodiment 6 | Ca | Calcium nitrate | The HY zeolite | 20 | 12 | 8 |
| Embodiment 7 | Zn | Zinc nitrate | The HMCM-49 zeolite | 21 | 15 | 5 |
| Embodiment 8 | W | Ammonium metatungstate | Modenite | 20 | 10 | 5 |
| Embodiment 9 | Fe | Ferric nitrate | The HMCM-22 zeolite | 20 | 18 | 3 |
Immersion process for preparing catalyst: the solubility salt aqueous solution of preparing certain density nickel nitrate aqueous solution, ammonium molybdate solution and component X, flood than adding in the catalyst carrier according to certain metering, then 110 ℃ dry 12 hours down, 550 ℃ of following roastings 6 hours.Reduce to room temperature after roasting finishes, in the reactor of packing into, 480 ℃ with hydrogen reducing 4 hours, is adjusted to the required condition of reaction after reduction finishes.The composition of catalyst among each embodiment, the starting material kind of component X sees Table 2.
The Ni-Mo-X/A loaded catalyst of table 2 immersion process for preparing is formed
| Embodiment | Component X | The starting material of component X | Carrier | Ni content, % (quality) | Mo content, % (quality) | X content, % (quality) |
| Embodiment 10 | Co | Cobalt nitrate | Al 2O 3 | 20 | 12 | 2.5 |
| Embodiment 11 | Mn | Manganese nitrate | SiO 2 | 22 | 15 | 3 |
| Embodiment 12 | Cu | Copper nitrate | Amorphous silicon aluminium | 20 | 10 | 3 |
| Embodiment 13 | Cr | Chromic nitrate | Modenite | 22 | 11 | 5 |
| Embodiment 14 | Ca | Calcium nitrate | The HY zeolite | 20 | 15 | 6 |
| Embodiment 15 | Zn | Zinc nitrate | The HMCM-49 zeolite | 20 | 15 | 8 |
| Embodiment 16 | W | Ammonium metatungstate | Modenite | 20 | 10 | 8 |
| Embodiment 17 | Fe | Ferric nitrate | The HMCM-22 zeolite | 20 | 18 | 5 |
The reactivity evaluation of catalyst: 180 grams and 100 are restrained one, two section fixed-bed tube reactor that catalyst are respectively charged into series connection.Enter the first stage reactor reaction after the 3-hydroxy propanal aqueous solution of raw material 10% (quality) and the hydrogen mixing preheating, entering second stage reactor after the first stage reactor outlet material heats up reacts, product behind the hydrogenation is after gas-liquid separation, form with gas chromatographic analysis, calculate reaction conversion ratio and selectivity.Reaction condition and reaction result concrete among each embodiment see Table 3.
The hydrogenation conditions of the various catalyst of table 3 and reaction result
| Embodiment | One anti-temperature, ℃ | Two anti-temperature, ℃ | Hydrogen Vapor Pressure, MPa | Hydrogen/3-hydroxy propanal (mole) | One anti-air speed, h -1 | Two anti-air speeds, h -1 | Conversion ratio, % | Selectivity, % |
| Embodiment 1 | 50 | 120 | 5.0 | 6.0 | 2.0 | 3.6 | 100 | 99.5 |
| Embodiment 2 | 50 | 120 | 4.0 | 5.5 | 3.0 | 5.4 | 100 | 98.7 |
| Embodiment 3 | 50 | 120 | 6.0 | 7.0 | 2.0 | 3.6 | 99.8 | 99.2 |
| Embodiment 4 | 50 | 120 | 10.0 | 6.0 | 3.6 | 3.6 | 100 | 99.3 |
| Embodiment 5 | 50 | 110 | 5.0 | 6.0 | 2.0 | 3.6 | 100 | 99.8 |
| Embodiment 6 | 50 | 110 | 5.0 | 6.0 | 3.6 | 3.6 | 100 | 99.1 |
| Embodiment 7 | 50 | 110 | 5.0 | 6.0 | 2.0 | 3.6 | 99.4 | 99.5 |
| Embodiment 8 | 50 | 120 | 5.0 | 5.0 | 2.0 | 3.6 | 100 | 99.2 |
| Embodiment 9 | 45 | 120 | 5.0 | 6.0 | 2.0 | 3.6 | 99.7 | 98.9 |
| Embodiment 10 | 45 | 120 | 5.0 | 6.0 | 2.0 | 3.6 | 100 | 99.6 |
| Embodiment 11 | 45 | 110 | 5.0 | 6.0 | 3.0 | 3.6 | 100 | 99.5 |
| Embodiment 12 | 50 | 120 | 5.0 | 6.0 | 2.0 | 3.6 | 100 | 99.9 |
| Embodiment 13 | 50 | 120 | 5.0 | 6.0 | 2.0 | 3.6 | 100 | 99.5 |
| Embodiment 14 | 50 | 120 | 5.0 | 6.0 | 2.0 | 3.6 | 100 | 99.2 |
| Embodiment 15 | 50 | 120 | 5.0 | 6.0 | 2.0 | 3.6 | 100 | 99.4 |
| Embodiment 16 | 50 | 120 | 5.0 | 6.0 | 2.0 | 3.6 | 100 | 99.1 |
| Embodiment 17 | 50 | 120 | 5.0 | 6.0 | 2.0 | 3.6 | 100 | 99.8 |
In the table, an anti-temperature is one section reaction temperature, and two anti-temperature are the second-stage reaction temperature, and an anti-air speed is one section reaction velocity, and two anti-air speeds are the second-stage reaction air speed.
Embodiment 18
Catalyst among the embodiment 11 180 gram and 100 gram catalyst are respectively charged into one, two section fixed-bed tube reactor of series connection, and 450 ℃ with hydrogen reducing 4 hours, cools the temperature to 50 ℃ after the reduction end.Enter the first stage reactor reaction after the 3-hydroxy propanal aqueous solution of raw material 10% (quality) and the hydrogen mixing preheating, enter second stage reactor after the first stage reactor outlet material heats up and react.The one-stage hydrogenation reaction condition is 50 ℃ of reaction temperatures, reaction pressure 5.0MPa, 3-hydroxy propanal aqueous solution air speed 2.0h
-1, H
2/ 3-hydroxy propanal mol ratio 4: 1; Second section hydrogenation conditions is that 120 ℃ of reaction temperatures, reaction pressure 5.0MPa, 3-hydroxy propanal aqueous solution air speed are 3.6h
-1, H
2/ 3-hydroxy propanal mol ratio is 8: 1.Conversion ratio and selectivity see Table 4 over time.
Table 4 22%Ni-15%Mo-3%Mn/SiO
2The hydroxy propanal hydrogenation reaction stability of catalyst
| React running time, hour | Conversion ratio, % | Selectivity, % |
| 24 | 100 | 99.8 |
| 100 | 100 | 99.5 |
| 300 | 100 | 99.4 |
| 500 | 100 | 99.5 |
| 800 | 100 | 99.3 |
| 1000 | 100 | 99.5 |
| 1500 | 100 | 99.4 |
Comparing embodiment 1
Prepare catalyst according to mixing method, adjust the addition of nickel nitrate and ammonium molybdate, make that nickel content is 20% (quality) in the catalyst of final acquisition, molybdenum content is 2% (quality).Catalyst 180 gram and 100 gram catalyst are respectively charged into one, two section fixed-bed tube reactor of series connection, and 450 ℃ with hydrogen reducing 4 hours, cools the temperature to 50 ℃ after the reduction end.Enter the first stage reactor reaction after the 3-hydroxy propanal aqueous solution of raw material 10% (quality) and the hydrogen mixing preheating, enter second stage reactor after the first stage reactor outlet material heats up and react.The one-stage hydrogenation reaction condition is 50 ℃ of reaction temperatures, reaction pressure 5.0MPa, 3-hydroxy propanal aqueous solution air speed 2.0h
-1, H
2/ 3-hydroxy propanal mol ratio 4: 1; Second section hydrogenation conditions is that 120 ℃ of reaction temperatures, reaction pressure 5.0MPa, 3-hydroxy propanal aqueous solution air speed are 3.6h
-1, H
2/ 3-hydroxy propanal mol ratio is 8: 1.Conversion ratio and selectivity see Table 5 over time.
Table 5 20%Ni-2%Mo/SiO
2The hydroxy propanal hydrogenation reaction stability of catalyst
| React running time, hour | Conversion ratio, % | Selectivity, % |
| 12 | 100 | 99.1 |
| 100 | 97.4 | 98.5 |
| 300 | 96.5 | 98.2 |
| 500 | 85.6 | 90.5 |
Claims (6)
1, a kind of 3-3-hydroxyl propionaldehyde hydrogenation to produce is equipped with 1, the catalyst of ammediol, it is characterized in that this catalyst is the Ni-Mo-X/A loaded catalyst, the mass fraction of Ni is 9%～38% in the catalyst, the mass fraction of Mo is 7%～45%, the mass fraction of component X is 1%～10%, and catalyst need reduce processing before use.
2, catalyst according to claim 1, it is characterized in that component X in the catalyst is any among Co, Mn, Cu, Cr, Ca, Zn, Fe or the W, carrier A is molecular sieve ZSM-5, MCM-49, MCM-22, SAPO-11, SAPO-34, modenite, β zeolite, L zeolite, Y zeolite, overstable gamma zeolite or oxide γ-Al
2O
3, SiO
2, any in MgO or the amorphous aluminum silicate or their mixture, catalyst needs reduce in hydrogen before use, reducing condition is Hydrogen Vapor Pressure 0.2～10.0MPa, hydrogen gas space velocity 200～1500h
-1, 300～500 ℃ of reduction temperatures, 2～20 hours recovery times.
3, catalyst according to claim 1 and 2, catalyst carrier are molecular sieve ZSM-5, MCM-49, SAPO-34, modenite, β zeolite or γ-Al
2O
3, SiO
2Or any in the amorphous aluminum silicate or their mixture.
4, catalyst according to claim 1 and 2, the mass fraction that it is characterized in that Ni in the catalyst is 10%～25%, and the mass fraction of component Mo is 8%～20%, and the mass fraction of component X is 3%～8%.
5, catalyst according to claim 1 and 2, the reducing condition that it is characterized in that catalyst are Hydrogen Vapor Pressure 2.0～8.0MPa, hydrogen gas space velocity 300～1000h
-1, 350～500 ℃ of reduction temperatures, 5～15 hours recovery times.
6, Preparation of catalysts method according to claim 1 and 2 is characterized in that catalyst is infusion process or mixing method preparation.
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| CN105709778A (en) * | 2014-12-05 | 2016-06-29 | 上海华谊能源化工有限公司 | Catalyst for catalytic hydrogenation of 3-hydroxyl propionaldehyde to prepare 1,3-propylene glycol, preparation method and applications thereof |
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| CN105709778B (en) * | 2014-12-05 | 2020-02-07 | 上海华谊能源化工有限公司 | Catalyst for preparing 1, 3-propylene glycol by catalytic hydrogenation of 3-hydroxypropionaldehyde and preparation method and application thereof |
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| CN104971733A (en) * | 2015-06-29 | 2015-10-14 | 黄河三角洲京博化工研究院有限公司 | Catalyst for 2-propyl-1-heptanol synthesis |
| CN110180551A (en) * | 2019-06-13 | 2019-08-30 | 湖南科技学院 | A kind of catalyst converting animal and plant fat to phase change heat storage material |
| CN112457158A (en) * | 2020-11-10 | 2021-03-09 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation of 3-hydroxypropionaldehyde and preparation method thereof |
| CN112457158B (en) * | 2020-11-10 | 2022-09-13 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation of 3-hydroxypropionaldehyde and preparation method thereof |
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Effective date of registration: 20170210 Address after: 201424 Fengxian District Cang Road, lane, Lane 357, room 100, room 295 Patentee after: Shanghai Hua Yi new material Co., Ltd Address before: 200137 Pudong North Road, Shanghai, No. 2031, No. Patentee before: Shanghai Huayi Acrylic Acid Co., Ltd. |