CN109806883A - Catalyst, with the method and system for use in carrying of catalyst preparation 3- aminopropanol - Google Patents
Catalyst, with the method and system for use in carrying of catalyst preparation 3- aminopropanol Download PDFInfo
- Publication number
- CN109806883A CN109806883A CN201910075213.3A CN201910075213A CN109806883A CN 109806883 A CN109806883 A CN 109806883A CN 201910075213 A CN201910075213 A CN 201910075213A CN 109806883 A CN109806883 A CN 109806883A
- Authority
- CN
- China
- Prior art keywords
- hydroxypropionitrile
- aminopropanol
- catalyst
- supported
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of supported, heterogeneous catalyst, including main active component, auxiliary agent and carrier, or including main active component and carrier, the simple substance of one or more of auxiliary agent Fe, Cu, Ru, Re, K, Zn or B or its oxide；Carrier is one or more of graphite, active carbon, carbon nanotube, graphene, silica, aluminum oxide, molecular sieve, titanium dioxide, zirconium dioxide, and the supported, heterogeneous catalyst is using ultrasonic load method preparation.Utilize catalyst preparation 3- aminopropanol of the invention, (1) the quality space-time yield of 3- aminopropanol is improved, (2) selectivity of 3- aminopropanol is improved, (3) reaction is realized can under lower reaction pressure, (4) stability of catalyst system is improved, (5) flow operations are simple, facilitate feasible, reduce production and later separation device one-time investment and production cost, it is easy to accomplish extensive continuous industrial production.
Description
Technical field
It is set the present invention relates to a kind of catalyst and using the method and system for use in carrying of catalyst preparation 3- aminopropanol
It is standby, belong to technical field of chemical synthesis.
Background technique
3- aminopropanol is a kind of important pharmaceutical intermediate, it medicine, pesticide, in terms of have widely
Purposes the drugs such as can pacify for synthesizing cyclophosphamide, the heart, and in addition it is the raw material for synthesizing vitamin B (DL-panthenol).In recent years
With the raising of social development levels, application of the panthenol in daily chemical products is continuously improved, and is especially produced in cosmetics and hair washing
Application in product is more and more wider, has greatly driven the market demand of 3- aminopropanol.
Chinese patent application 201110289735.7 report it is a kind of using with 1,4-butyrolactone as raw material, in the work of hydrazine hydrate
With lower open loop, sodium nitrite in aqueous solution is added and generates acid azide, then occurs to reset the method for generating 3- aminopropanol.The party
Not only process is complicated for method, and target product 3- aminopropanol yield is lower, is not suitable for practical application and promotes.Feng Xiaoliang is reported
Then one kind is condensed using cyclohexanone as Material synthesis cyclohexanone oxime with acrylonitrile, then crack preparation 3- amino by catalytic hydrogenation
The method of propyl alcohol.This method equally exists complex steps, target product poor selectivity, the low problem of product yield.
Patent CH-B-244837, DE-B-2655794, EP-A1-1132371, JP-A-2002201164 etc. report one
Kind is using 3- hydroxypropionitrile as raw material, and react under the conditions of facing ammonia with hydrogen the method for generating 3- aminopropanol.This method can
One step directly synthesizes target product 3- aminopropanol, but still remains the selectively low problem of target product.JP-A-
05163213, which discloses a kind of Raney cobalt catalyst, faces the reaction of ammonia hydrogenation synthesis 3- aminopropanol, the catalysis for 3- hydroxypropionitrile
System risk is high, is not easy to realize industrial applications.Patent CN-A-103261148 report it is a kind of production and purification 3- ammonia
The method of base propyl alcohol, the selectivity of 3- aminopropanol is up to 93%, but reaction pressure is up to 18MPa, and quality space-time yield is only
For 0.3Kg/Kgh-1.Also the report of catalyst life is had no in above-mentioned synthesis 3- aminopropanol patent.Therefore, above-mentioned report
Catalyst has being difficult to use in that continuous production or activity are low, the service life is short and severe reaction conditions, industrial application value are low.
3- hydroxypropionitrile faces under the conditions of ammonia plus hydroformylation step directly synthesize that 3- aminopropanol process is simple, and target product is selective
Height is a relatively environmentally protective path for preparing 3- aminopropanol.There is currently main problem be reaction condition it is severe
The problem of quarter, poor catalyst stability, active low one or more aspects.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of catalyst, which passes through ultrasonic load method preparation,
Active high, selectivity is good, using catalyst preparation 3- aminopropanol, can carry out at low pressures, high conversion rate, system used
System ensure that going on smoothly for reaction.
In order to solve the above-mentioned technical problem, the present invention discloses a kind of supported, heterogeneous catalyst, including main activity first
Component, auxiliary agent and carrier, or including main active component and carrier, the main active component is Ni and/or Co, and the auxiliary agent is
The simple substance of one or more of Fe, Cu, Ru, Re, K, Zn or B or its oxide；The carrier is insoluble solid material
Work stone ink, active carbon, carbon nanotube, graphene, silica, aluminum oxide, molecular sieve, titanium dioxide, in zirconium dioxide
One or more, which includes: using ultrasonic load method preparation, step
(1), by the soluble-salt deionized water dissolving of the soluble-salt or main active component of main active component and auxiliary agent
Salting liquid is obtained, wherein ion concentration is 0.05-2.0mol/L；
(2), quantitative carrier is weighed to be placed in salting liquid obtained by step (1) and be transferred in ultrasonic reactor at 5-120KHz
Reason t hours, 0 t≤10 <, preferably 0.1≤t≤2；
(3), pH value will be adjusted in the solution where ammonia spirit addition step (2) is 9~11, and is continued at ultrasonic treatment
Reason t2 hours, 0 t2≤8 <, preferably 0.1 t2≤1.5 <；
(4), by obtained mixture after step (3) ultrasound in 60~100 DEG C of ammonia still processs to mixture ph be 5~7；
(5), filter, with deionized water or ethanol washing step (4) products obtained therefrom, then in 60~120 DEG C dry 3~
24h；350~700 DEG C of roasting 2-10h in Muffle furnace are obtained through ultrasound load treated supported, heterogeneous catalyst.
Further, the mass fraction of the main active component be 0.5%-50%, preferably 5%~25%；The matter of auxiliary agent
Measuring score is 0%~20%, preferably 0%~5%；Surplus is carrier.
Further, the carrier is the one or two of silica or aluminum oxide.
The invention also discloses a kind of methods using aforementioned supported, heterogeneous catalyst preparation 3- aminopropanol, with 3- hydroxyl
Base propionitrile is that raw material hydrogenation occurs under liquefied ammonia existence condition prepares 3- aminopropanol, by 3- hydroxypropionitrile and liquefied ammonia by than
After example mixing, then mix with hydrogen, then at 60~230 DEG C, preferably 80~120 DEG C, reaction pressure is 1.0~30.0MPa
Under the conditions of, preferably 2.0~18.0MPa；Reaction in the presence of the supported, heterogeneous catalyst being prepared through ultrasonic load method
It is reacted in device and obtains product.
Further, the addition molar ratio of the liquefied ammonia and 3- hydroxypropionitrile is 1:1~30:1, preferably 2:1~15:1.
Further, the addition molar ratio of the hydrogen and 3- hydroxypropionitrile is 1:1~10:1, preferably 2:1~5:1.
Further, the liquid quality air speed of the 3- hydroxypropionitrile is 0.1~1.0h-1, preferably 0.9~1.0h-1。
Further, the reactor is one of fixed bed, fluidized bed or paste state bed reactor, and preferably fixed bed is anti-
Answer device.
Further, the supported, heterogeneous catalyst is activated using preceding by hydrogen reducing, and the hydrogen is also
The condition that original is activated is under 300~450 DEG C of temperature, 0.1~1.0MPa of pressure, with volume space velocity for 500~3000h-1
Hydrogen stream reduction 1~for 24 hours, preferably 2~8h.
System used in the method for 3- aminopropanol, 3- hydroxyl third are prepared using aforementioned catalytic agent invention additionally discloses a kind of
Nitrile passes sequentially through raw mixture filter with the raw material mixing vessel of liquefied ammonia mixing, high-pressure pump is connected to mixer；Hydrogen gas tank
Pass sequentially through purification pot, hydrogen filter, check valve connection mixer；The discharge port connection of mixer is filled with supported, heterogeneous
The discharge port of the reactor of catalyst, reactor is connected to collecting tank；The collecting tank also passes through counterbalance valve and is connected with gas-chromatography
Instrument；It is provided with emergent evacuation pipe between high-pressure pump and mixer, one end of gas chromatograph is provided with evacuated tube；In hydrogen
It is additionally provided with pressure gauge, pressure-regulating valve and mass flowmenter between tank and mixer, is also set up in front of gas chromatograph
There is spinner flowmeter, several shut-off valves are also set up on the system pipeline.
Catalyst of the invention is prepared through ultrasonic load method, is the catalyst of high dispersive type.In such loaded catalyst
In, catalytic activity is higher when Co is as main active component, but more expensive；And Ni relative price is cheap, but when as main active component
Effect is not so good as Co, and the present invention passes through ultrasonic load method, and uses reasonable preparation parameter, when making active component main using Ni,
The catalytic activity as Co is reached.Using catalyst preparation 3- aminopropanol of the invention, generally (1) improves 3- ammonia
The quality space-time yield of base propyl alcohol, (2) improve the selectivity of target product 3- aminopropanol, and (3) make 3- hydroxypropionitrile face ammonia
Hydrogenation reaction can realize that (4) improve the stability of catalyst system under lower reaction pressure, and (5) flow operations are simple, convenient
It is feasible, reduce production and later separation device one-time investment and production cost, it is easy to accomplish extensive continuous industry metaplasia
It produces.Reaction pressure range when prepared by 3- aminopropanol is larger, may be implemented especially relative to the prior art lower than 18.0MPa
Reaction pressure, safety is significantly greatly increased.
Detailed description of the invention
Fig. 1 shows flow diagram according to an embodiment of the present invention.
In figure: 1 shut-off valve；2- pressure gauge；3- purification pot；4- shut-off valve；5- pressure-regulating valve；6- shut-off valve；7- hydrogen
Filter；8- mass flowmenter；9- check valve；10- mixer；11- shut-off valve；12- high-pressure pump；The filtering of 13- raw mixture
Device；14- shut-off valve；15- reactor；16- shut-off valve；17- collecting tank；18- shut-off valve；19- counterbalance valve；20- shut-off valve；21-
Shut-off valve；22- spinner flowmeter；23- gas chromatograph；24- hydrogen gas tank；25- raw material mixing vessel.
Specific embodiment
Below with reference to embodiment, more specifically the elaboration contents of the present invention.Implementation of the invention is not limited to following reality
Example is applied, the accommodation in any form made to the present invention or changed all should be within the scope of the present invention.
Below by specific embodiment, the present invention will be further described.
System for use in carrying of the present invention
As shown in Figure 1, the hydrogen gas tank 24 equipped with hydrogen is by piping connection mixer 10, hydrogen gas tank and mixer 10 it
Between pipeline on be disposed with shut-off valve 1, pressure gauge 2, purification pot 3, shut-off valve 4, pressure-regulating valve 5, shut-off valve 6, hydrogen
Filter 7, mass flowmenter 8, check valve 9.
Raw material mixing vessel 25 for mixing 3- hydroxypropionitrile and liquefied ammonia is by pipeline connection mixer 10, in raw material
Raw material filter 13, high-pressure pump 12, shut-off valve 11 are also disposed on pipeline between mixing vessel 25 and mixer 10, it is high
Press pump 12 squeezes into 3- hydroxypropionitrile and liquefied ammonia mixing liquid in mixer 10, is also connected between shut-off valve 11 and high-pressure pump 12
There is emergency discharging pipe, shut-off valve 14 is provided on the emergency discharging pipe.
Reactor 15, shut-off valve 16 and collecting tank 17 are connected in turn by pipeline in the discharge port of mixer 10, reacted
The supported, heterogeneous catalyst that the present invention is prepared through ultrasonic load method, hydrogen, 3- hydroxypropionitrile and liquid are filled in device 15
It after ammonia mixes in mixer 10, is reacted in reactor 15, the reactor 15 of following example 1-15 uses fixed bed
Reactor, long 60mm, internal diameter 10mm.The feed inlet of collecting tank 17 is set to top, reacts resulting liquid product for collecting,
The liquid product is released by shut-off valve 16.The top of collecting tank 17 also passes through piping connection gas chromatograph 23, and gas is from collection
The top of tank 17 successively by the counterbalance valve 19, shut-off valve 20, the spinner flowmeter 22 that are set on pipeline, reaches gas chromatograph
23 analysis gaseous products.It has been arranged in parallel shut-off valve 21 with spinner flowmeter 22 and gas chromatograph 23, has passed through the shut-off valve 21
Controllable gas emptying is absorbed or is recycled.
The bottom of collecting tank 17 is provided with the sampling pipe with shut-off valve 18, gas phase color can be passed through after reaction product sampling
Spectrometer 23 carries out on-line analysis.
Group becomes 20Ni-3Re/SiO2Catalyst preparation:
Weigh 7.432gNi (NO3)2·6H2O and 0.432g NH4·ReO4It is dissolved in 150mL deionized water；Then it weighs
10.0g SiO2It is placed in above-mentioned mixed solution, stirs, be transferred in ultrasonic reactor, 1h is ultrasonically treated with 50KHz；Measure matter
Measuring concentration is that 28% ammonia spirit 17mL is added in above-mentioned mixed solution, and continuation is ultrasonically treated 1h at primary frequency 50KHz；Then
By said mixture in 90 DEG C of ammonia still processs to mixture ph be 6.5 or so；It filters, products obtained therefrom is washed with deionized, then
In 120 DEG C of dry 4h；4h is roasted in Muffle furnace 450 DEG C.Catalyst breakage is spare to 20~40 mesh, other composition catalysis
Agent can be prepared according to different proportion with Tongfang method.
Loaded catalyst of the invention is 5mL, is handled using preceding by hydrogen reducing to be activated, preferable hydrogen
Gas reduction activation condition is (normal pressure, volume space velocity 1500h in 390 DEG C of hydrogen stream-1) reduction 6 hours.
The preparation of 3- aminopropanol:
The product that the present invention obtains is analyzed using Agilent7890B, DB-35 capillary chromatographic column, fid detector.
Embodiment 1
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio for 5:1, by mixed liquid after then bed reaction system to be fixed is stablized
It is squeezed into mixer 10 through high-pressure pump 12, adjusts the liquid quality air speed of 3- hydroxypropionitrile as 1.0 3- hydroxypropionitrile g/ catalysis
Agent gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 2.0:1 in reaction system, is reacted, and the reaction time is 48 hours,
Gas chromatography analysis is passed through by the sampling of collecting tank 17.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 90%, selectivity
93%.
Embodiment 2
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio for 5:1, by mixed liquid after then bed reaction system to be fixed is stablized
It is squeezed into mixer 10 through high-pressure pump 12, adjusts the liquid quality air speed of 3- hydroxypropionitrile as 1.0 3- hydroxypropionitrile g/ catalysis
Agent gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 2.2:1 in reaction system, is reacted, and the reaction time is 48 hours,
Gas chromatography analysis is passed through by the sampling of collecting tank 17.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 93%, selectivity
92%.
Embodiment 3
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio for 5:1, by mixed liquid after then bed reaction system to be fixed is stablized
It is squeezed into mixer 10 through high-pressure pump 12, adjusts the liquid quality air speed of 3- hydroxypropionitrile as 1.0 3- hydroxypropionitrile g/ catalysis
Agent gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 2.5:1 in reaction system, is reacted, and the reaction time is 48 hours,
Gas chromatography analysis is passed through by the sampling of collecting tank 17.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 96%, selectivity
90%.
Embodiment 4
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio 5:1, then bed reaction system to be fixed passes through mixed liquid after stablizing
High-pressure pump 12 is squeezed into mixer 10, and the liquid quality air speed for adjusting 3- hydroxypropionitrile is 1.0 3- hydroxypropionitrile g/ catalyst
Gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 3.0:1 in reaction system, is reacted, and the reaction time is 48 hours, by receiving
The collection sampling of tank 17 passes through gas chromatography analysis.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 99.8%, selectivity 88%.
Embodiment 5
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio 5:1, then bed reaction system to be fixed passes through mixed liquid after stablizing
High-pressure pump 12 is squeezed into mixer 10, and the liquid quality air speed for adjusting 3- hydroxypropionitrile is 1.0 3- hydroxypropionitrile g/ catalyst
Gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 5.0:1 in reaction system, is reacted, and the reaction time is 48 hours, by receiving
The collection sampling of tank 17 passes through gas chromatography analysis.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 100%, selectivity 85%.
Embodiment 6
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 3.0MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 105 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio 5:1, then bed reaction system to be fixed passes through mixed liquid after stablizing
High-pressure pump 12 is squeezed into mixer 10, and the liquid quality air speed for adjusting 3- hydroxypropionitrile is 1.0 3- hydroxypropionitrile g/ catalyst
Gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 2.0:1 in reaction system, is reacted, and the reaction time is 48 hours, by receiving
The collection sampling of tank 17 passes through gas chromatography analysis.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 96%, selectivity 88%.
Embodiment 7
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 110 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio 5:1, then bed reaction system to be fixed passes through mixed liquid after stablizing
High-pressure pump 12 is squeezed into mixer 10, and the liquid quality air speed for adjusting 3- hydroxypropionitrile is 1.0 3- hydroxypropionitrile g/ catalyst
Gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 2.0:1 in reaction system, is reacted, and the reaction time is 48 hours, by receiving
The collection sampling of tank 17 passes through gas chromatography analysis.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 98%, selectivity 83%.
Embodiment 8
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio 5:1, then bed reaction system to be fixed passes through mixed liquid after stablizing
High-pressure pump 12 is squeezed into mixer 10, and the liquid quality air speed for adjusting 3- hydroxypropionitrile is 1.0 3- hydroxypropionitrile g/ catalyst
Gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 2.0:1 in reaction system, is reacted, and the reaction time is 48 hours, by receiving
The collection sampling of tank 17 passes through gas chromatography analysis.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 96%, selectivity 83%.
Embodiment 9
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio 5:1, then bed reaction system to be fixed passes through mixed liquid after stablizing
High-pressure pump 12 is squeezed into mixer 10, and the liquid quality air speed for adjusting 3- hydroxypropionitrile is 1.0 3- hydroxypropionitrile g/ catalyst
Gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 3.0:1 in reaction system, is reacted, and the reaction time is 48 hours, by receiving
The collection sampling of tank 17 passes through gas chromatography analysis.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 98.5%, selectivity 82%.
Embodiment 10
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio 5:1, then bed reaction system to be fixed passes through mixed liquid after stablizing
High-pressure pump 12 is squeezed into mixer 10, and the liquid quality air speed for adjusting 3- hydroxypropionitrile is 0.9 3- hydroxypropionitrile g/ catalyst
Gh, H in reaction system2Hydrogen/3- hydroxypropionitrile molar ratio is 2.5:1, is reacted, and the reaction time is 48 hours, by
The sampling of collecting tank 17 passes through gas chromatography analysis.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 100%, selectivity 90%.
Embodiment 11
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio 6:1, then bed reaction system to be fixed passes through mixed liquid after stablizing
High-pressure pump 12 is squeezed into mixer 10, and the liquid quality air speed for adjusting 3- hydroxypropionitrile is 0.9 3- hydroxypropionitrile g/ catalyst
Gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 2.5:1 in reaction system, is reacted, and the reaction time is 48 hours, by receiving
The collection sampling of tank 17 passes through gas chromatography analysis.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 100%, selectivity 92%.
Embodiment 12
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio 8:1, then bed reaction system to be fixed passes through mixed liquid after stablizing
High-pressure pump 12 is squeezed into mixer 10, and the liquid quality air speed for adjusting 3- hydroxypropionitrile is 0.9 3- hydroxypropionitrile g/ catalyst
Gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 2.5:1 in reaction system, is reacted, and the reaction time is 48 hours, by receiving
The collection sampling of tank 17 passes through gas chromatography analysis.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 100%, selectivity 94%.
Embodiment 13
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio 8:1, then bed reaction system to be fixed passes through mixed liquid after stablizing
Pump is squeezed into mixer, and the liquid quality air speed for adjusting 3- hydroxypropionitrile is 0.9 3- hydroxypropionitrile g/ catalyst gh, instead
Answering the molar ratio of hydrogen and 3- hydroxypropionitrile in system is 2.5:1, is reacted, and the reaction time is 48 hours, by collecting tank 17
Sampling passes through gas chromatography analysis.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 100%, selectivity 97%.
Embodiment 14
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio for 10:1, by mixed liquid after then bed reaction system to be fixed is stablized
It is squeezed into mixer 10 through high-pressure pump 12, adjusts the liquid quality air speed of 3- hydroxypropionitrile as 0.9 3- hydroxypropionitrile g/ catalysis
Agent gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 2.5:1 in reaction system, is reacted, and the reaction time is 48 hours,
Gas chromatography analysis is passed through by the sampling of collecting tank 17.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 100%, selectivity
98.5%.
Embodiment 15
Weigh above-mentioned 20Ni-3Re/SiO2Catalyst 2.6g (about 5ml), is fitted into fixed bed reactors.Catalyst makes
With preceding, activated by hydrogenation treatment, activation condition are as follows: T=390 DEG C of temperature；Pressure P is 0.3MPa, gas volume air speed GHSV
=1500h-1, the recovery time 6 hours.When reactor temperature Temperature fall is to 100 DEG C, 8MPa is boosted to, waiting system is stablized.
Liquefied ammonia is mixed with 3- hydroxypropionitrile with molar ratio 10:1, then bed reaction system to be fixed passes through mixed liquid after stablizing
High-pressure pump 12 is squeezed into mixer 10, and the liquid quality air speed for adjusting 3- hydroxypropionitrile is 0.9 3- hydroxypropionitrile g/ catalyst
Gh, the molar ratio of hydrogen and 3- hydroxypropionitrile is 2.5:1 in reaction system, is reacted, and the reaction time is 1000 hours, often
Gas chromatography analysis is passed through by the sampling of collecting tank 17 every 24 hours.3- hydroxypropionitrile faces ammonia hydrogenation reaction, conversion ratio 100%,
Selectivity 98.5%.
Above to the present invention have been described in detail, but the invention is not limited to specific embodiment parties described herein
Formula.
Claims (10)
1. a kind of supported, heterogeneous catalyst, including main active component, auxiliary agent and carrier, or including main active component and carrier,
The main active component is Ni and/or Co, and the auxiliary agent is the list of one or more of Fe, Cu, Ru, Re, K, Zn or B
Matter or its oxide；The carrier is insoluble solid material graphite, active carbon, carbon nanotube, graphene, silica, three
One or more of Al 2 O, molecular sieve, titanium dioxide, zirconium dioxide, it is characterised in that: the supported, heterogeneous is urged
Agent is prepared using ultrasonic load method, and step includes:
(1), that the soluble of the soluble-salt or main active component of main active component and auxiliary agent is obtained salt with deionized water dissolving is molten
Liquid, wherein ion concentration is 0.05-2.0mol/L；
(2), quantitative carrier is weighed to be placed in salting liquid obtained by step (1) and be transferred to 5-120KHz processing t1 in ultrasonic reactor
Hour, 0 t1≤10 <；
(3), will ammonia spirit be added step (2) where solution in adjust pH value be 9~11, and continue be ultrasonically treated t2 it is small
When, 0 t2≤8 <；
(4), by obtained mixture after step (3) ultrasound in 60~100 DEG C of ammonia still processs to mixture ph be 5~7；
(5), filter, with deionized water or ethanol washing step (4) products obtained therefrom, then in 60~120 DEG C dry 3~for 24 hours；Again
350~700 DEG C of 2~10h of roasting in Muffle furnace are obtained through ultrasound load treated supported, heterogeneous catalyst.
2. supported, heterogeneous catalyst according to claim 1, it is characterised in that: the mass fraction of the main active component is
0.5%~50%；The mass fraction of auxiliary agent is 0%~20%；Surplus is carrier.
3. supported, heterogeneous catalyst according to claim 1 or claim 2, it is characterised in that: the carrier is silica or three
The one or two of Al 2 O.
4. a kind of utilize supported, heterogeneous catalyst preparation 3- aminopropanol described in claim 1-3 any one claim
Method, hydrogenation preparation 3- aminopropanol occurs under liquefied ammonia existence condition using 3- hydroxypropionitrile as raw material, feature exists
In: it after 3- hydroxypropionitrile and liquefied ammonia are mixed in proportion, then mixes with hydrogen, then at 60~230 DEG C, reaction pressure is
It is anti-in the reactor in the presence of supported, heterogeneous catalyst being prepared through ultrasonic load method under the conditions of 1.0~30.0MPa
It answers and obtains product.
5. preparing the method for 3- aminopropanol according to claim 4, it is characterised in that: the liquefied ammonia and 3- hydroxypropionitrile
Addition molar ratio is 1:1~30:1.
6. preparing the method for 3- aminopropanol according to claim 4, it is characterised in that: the hydrogen and 3- hydroxypropionitrile
Addition molar ratio is 1:1~10:1.
7. preparing the method for 3- aminopropanol according to claim 4, it is characterised in that: the liquid matter of the 3- hydroxypropionitrile
Amount air speed is 0.1~1.0h-1。
8. preparing the method for 3- aminopropanol according to claim 4, it is characterised in that: the reactor is fixed bed, stream
Change one of bed or paste state bed reactor.
9. preparing the method for 3- aminopropanol according to claim 4, it is characterised in that: the supported, heterogeneous catalyst exists
It is activated using preceding by hydrogen reducing, the condition that the hydrogen reducing is activated is the pressure at 300~450 DEG C of temperature
Under 0.1~1.0MPa, with volume space velocity for 500~3000h-1Hydrogen stream reduction 1~for 24 hours.
10. system used in the method for 3- aminopropanol is prepared described in a kind of claim 4-9 any one claim, it is special
Sign is: the raw material mixing vessel that 3- hydroxypropionitrile is mixed with liquefied ammonia passes sequentially through raw mixture filter, high-pressure pump connects
Logical mixer；Hydrogen gas tank passes sequentially through purification pot, hydrogen filter, check valve connection mixer；The discharge port of mixer is connected to
It is filled with the reactor of supported, heterogeneous catalyst, the discharge port of reactor is connected to collecting tank；The collecting tank also passes through back pressure
Valve is connected with gas chromatograph；It is provided with emergent evacuation pipe between high-pressure pump and mixer, is set in one end of gas chromatograph
It is equipped with evacuated tube；Pressure gauge, pressure-regulating valve and mass flowmenter are additionally provided between hydrogen gas tank and mixer, in gas phase
It is additionally provided with spinner flowmeter in front of chromatograph, several shut-off valves are also set up on the system pipeline.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910075213.3A CN109806883B (en) | 2019-01-25 | 2019-01-25 | Catalyst, method for preparing 3-aminopropanol by using catalyst and system used by method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910075213.3A CN109806883B (en) | 2019-01-25 | 2019-01-25 | Catalyst, method for preparing 3-aminopropanol by using catalyst and system used by method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109806883A true CN109806883A (en) | 2019-05-28 |
| CN109806883B CN109806883B (en) | 2021-12-24 |
Family
ID=66605255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910075213.3A Active CN109806883B (en) | 2019-01-25 | 2019-01-25 | Catalyst, method for preparing 3-aminopropanol by using catalyst and system used by method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109806883B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981738A (en) * | 2019-12-30 | 2020-04-10 | 杭州新本立医药有限公司 | Synthesis method of 2-aminopropanol |
| CN111153768A (en) * | 2020-01-21 | 2020-05-15 | 浙江师范大学 | Synthetic method of isohexide |
| CN111205192A (en) * | 2020-01-21 | 2020-05-29 | 新典化学材料(上海)有限公司 | Preparation method of N, N, N' -trimethyl bis (aminoethyl) ether |
| CN111229315A (en) * | 2020-01-21 | 2020-06-05 | 浙江师范大学 | Catalyst for synthesizing 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanol and preparation and application thereof |
| CN111253269A (en) * | 2020-03-16 | 2020-06-09 | 安庆市鑫富化工有限责任公司 | Crude steaming process of 3-aminopropanol |
| CN111991827A (en) * | 2020-08-20 | 2020-11-27 | 兄弟科技股份有限公司 | Production equipment and method for synthesizing 3-aminopropanol by continuous hydrogenation |
| CN116102437A (en) * | 2022-12-23 | 2023-05-12 | 南京红宝丽醇胺化学有限公司 | Preparation method of 3-aminopropanol |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1952054A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Process for preparation of hydrogenation catalyst composition |
| US20090137825A1 (en) * | 2006-04-04 | 2009-05-28 | Christophe Bauduin | Method of producing a carboxylic alkyl ester |
| CN103261148A (en) * | 2010-12-14 | 2013-08-21 | 巴斯夫欧洲公司 | Method for producing and purifying 3-minopropanol |
| CN105771989A (en) * | 2014-12-24 | 2016-07-20 | 高化学株式会社 | Copper-based catalyst and preparation method thereof |
| CN106179377A (en) * | 2015-04-30 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst compositions |
| CN106944065A (en) * | 2017-03-27 | 2017-07-14 | 江苏金聚合金材料有限公司 | The preparation method and application of graphene-supported nickel hydrogenation catalyst |
-
2019
- 2019-01-25 CN CN201910075213.3A patent/CN109806883B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1952054A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Process for preparation of hydrogenation catalyst composition |
| US20090137825A1 (en) * | 2006-04-04 | 2009-05-28 | Christophe Bauduin | Method of producing a carboxylic alkyl ester |
| CN103261148A (en) * | 2010-12-14 | 2013-08-21 | 巴斯夫欧洲公司 | Method for producing and purifying 3-minopropanol |
| CN105771989A (en) * | 2014-12-24 | 2016-07-20 | 高化学株式会社 | Copper-based catalyst and preparation method thereof |
| CN106179377A (en) * | 2015-04-30 | 2016-12-07 | 中国石油化工股份有限公司 | A kind of preparation method of Hydrobon catalyst compositions |
| CN106944065A (en) * | 2017-03-27 | 2017-07-14 | 江苏金聚合金材料有限公司 | The preparation method and application of graphene-supported nickel hydrogenation catalyst |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110981738A (en) * | 2019-12-30 | 2020-04-10 | 杭州新本立医药有限公司 | Synthesis method of 2-aminopropanol |
| CN110981738B (en) * | 2019-12-30 | 2022-09-20 | 杭州新本立医药有限公司 | Synthesis method of 2-aminopropanol |
| CN111153768A (en) * | 2020-01-21 | 2020-05-15 | 浙江师范大学 | Synthetic method of isohexide |
| CN111205192A (en) * | 2020-01-21 | 2020-05-29 | 新典化学材料(上海)有限公司 | Preparation method of N, N, N' -trimethyl bis (aminoethyl) ether |
| CN111229315A (en) * | 2020-01-21 | 2020-06-05 | 浙江师范大学 | Catalyst for synthesizing 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanol and preparation and application thereof |
| CN111229315B (en) * | 2020-01-21 | 2022-12-27 | 浙江师范大学 | Catalyst for synthesizing 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propanol and preparation and application thereof |
| CN111205192B (en) * | 2020-01-21 | 2023-01-13 | 新典化学材料(上海)有限公司 | Preparation method of N, N, N' -trimethyl bis (aminoethyl) ether |
| CN111153768B (en) * | 2020-01-21 | 2023-06-02 | 浙江师范大学 | Synthesis method of isohexide |
| CN111253269A (en) * | 2020-03-16 | 2020-06-09 | 安庆市鑫富化工有限责任公司 | Crude steaming process of 3-aminopropanol |
| CN111991827A (en) * | 2020-08-20 | 2020-11-27 | 兄弟科技股份有限公司 | Production equipment and method for synthesizing 3-aminopropanol by continuous hydrogenation |
| CN116102437A (en) * | 2022-12-23 | 2023-05-12 | 南京红宝丽醇胺化学有限公司 | Preparation method of 3-aminopropanol |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109806883B (en) | 2021-12-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109806883A (en) | Catalyst, with the method and system for use in carrying of catalyst preparation 3- aminopropanol | |
| CN109734601A (en) | A method of preparing 1,3- propane diamine | |
| CN105833864B (en) | A kind of support type nano spherical particle palladium catalyst and its preparation method and application | |
| US20100267989A1 (en) | Continuous preparation of amines by nitrile compound hydrogenation | |
| CN113354602B (en) | Method for preparing 2-methyltetrahydrofuran from furfural through one-step hydrogenation | |
| CN103539635B (en) | Method for preparing isopropyl alcohol by acetone hydrogenation | |
| CN101455963A (en) | Catalyst for preparing C2-C3 lower aliphatic amine and production method thereof | |
| CN108355716A (en) | A kind of Cu-BTC assemble nanometers metallic catalyst prepares and is used for CO2Formylation reaction | |
| CN106881085A (en) | The catalyst and preparation method and process for selective hydrogenation of hydroquinones hydrogenation | |
| CN113149850A (en) | Process for continuously preparing N-hydroxyethyl-1, 3-propane diamine by using micro-mixing and fixed bed reactor | |
| CN103007943A (en) | Catalyst used for preparing ethanol by hydrogenation of acetic ester as well as preparation method and application of catalyst | |
| CN103664649B (en) | Method for preparing monoethanolamine from ethylene glycol | |
| CN102229587B (en) | Method for generating succinic anhydride through maleic anhydride hydrogenation catalyzed by Nano-Ni | |
| CN113563213B (en) | Preparation method of 3, 5-diaminobenzoic acid | |
| CN101486667B (en) | Method for preparing cyclohexanone oxime by fluid bed reactor | |
| CN107963977A (en) | A kind of method that alpha-keto amide is prepared using micro-reaction device | |
| CN115155462A (en) | Method and device for preparing 2, 4-diaminoanisole by continuous catalytic hydrogenation | |
| CN108658787A (en) | The preparation method of ethamine | |
| CN107983363A (en) | It is continuous to prepare 1,2- propane diamine catalyst and preparation method thereof | |
| CN105001279B (en) | The method that isomalt is prepared by catalytic hydrogenation by isomaltoketose | |
| CN100408547C (en) | Preparation method of serinol | |
| CN110054547B (en) | Method for preparing ethanol by oxalate hydrogenation under coupled catalysis of integrated catalyst | |
| CN1078095C (en) | Amorphous alloy catalyst containing nickel and phosphorus and preparation method thereof | |
| CN108707061A (en) | A kind of technique that methanol is used for methyl acetate ethyl alcohol | |
| CN104370748B (en) | High selectivity produces the method for triethylamine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 321001 no.688, Yingbin Avenue, Jinhua City, Zhejiang Province Applicant after: ZHEJIANG NORMAL University Address before: 311231 Xiaoshan campus of Zhejiang Normal University, 1108 Gengwen Road, ningwei Town, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant before: ZHEJIANG NORMAL University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |