CN104399467B - A kind of method preparing oil hydrogenation catalyst at organic-aqueous system - Google Patents
A kind of method preparing oil hydrogenation catalyst at organic-aqueous system Download PDFInfo
- Publication number
- CN104399467B CN104399467B CN201410643222.5A CN201410643222A CN104399467B CN 104399467 B CN104399467 B CN 104399467B CN 201410643222 A CN201410643222 A CN 201410643222A CN 104399467 B CN104399467 B CN 104399467B
- Authority
- CN
- China
- Prior art keywords
- solution
- deionized water
- nickel
- catalyst
- isobutyl acetate
- 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.)
- Active
Links
Abstract
The invention discloses a kind of method preparing oil hydrogenation catalyst in organic water system.The method uses isobutyl acetate and water to be that medium carries out coprecipitation reaction and carries out distilling modified preparation with nickel as active component again, zirconium, magnesium or iron are auxiliary agent, aluminum oxide is the oil hydrogenation catalyst of carrier, account in terms of overall catalyst weight by each component, nickel 10 30wt%, alumina support 50 85wt%, auxiliary agent zirconium, magnesium or iron 0.01 10wt%, described alumina support specific surface area is 120 450cc/g, and pore volume is 1 2.7mm/g.Catalyst activity prepared by this method is high, use safely, be suitable to oil hydrogenation reaction.
Description
Technical field
The present invention relates to oil hydrogenation catalyst technical field, more specifically use organic-aqueous media to prepare
With nickel as active component, aluminum oxide is the method with highly active oil hydrogenation catalyst of carrier.
Background technology
The food source that the mankind are important is not only by grease, is also detergents and cosmetic, rubber plastic, textile printing and dyeing, change
Work coating and the important source material of medical industry.The grease of nature all contains one, two or more not
Saturated bond, Long Term Contact air pole is oxidizable, produces peroxide and is further decomposed into the aldehyde of short carbon chain, ketone, acid etc.
The compound of little molecule, has intense stimulus smell, causes spoiled by rancid oil or fat, is not suitable for using.
Consaturated oil improves oxygen and the stability of heat by hydrogenation under the effect of catalyst, reduces insatiable hunger
And degree, add solid fats content, be both easy to store, transport, improve again the color and luster of grease, fragrance and
Taste.
At present, the oil hydrogenation catalyst of domestic use is broadly divided into cell cube metallic catalyst, diploid metal
Catalyst and triplet metallic catalyst, classify in any case, and its main active is essentially all metallic nickel,
Add other metals a small amount of simultaneously and do skeleton as auxiliary agent, carrier many employings aluminum oxide, silica, diatomite
Support.CN1415413A, CN101554588A, CN1944610A are to the preparation of catalyst and carrying of activity
Height has all done the work being highly profitable.
Summary of the invention
The technical problem to be solved be overcome that prior art catalyst grain size is uneven, reactivity not
High problem, it is provided that a kind of organic-aqueous system prepares the method for oil hydrogenation catalyst.
The present invention is a kind of method preparing oil hydrogenation catalyst at organic-aqueous system, it is characterised in that institute
Stating oil hydrogenation catalyst is with aluminum oxide as carrier, and nickel is active component, and zirconium, magnesium or iron are auxiliary agent；Each group
Divide and account for overall catalyst weight meter, nickel 10-30wt%, alumina support 50-85wt%, auxiliary agent zirconium, magnesium or iron
0.01-10wt%, described alumina support specific surface area is 120-450m2/ g, pore volume is 1-2.7m3/g；Its
Described in alumina support and catalyst precursor be all to close in the aqueous solution containing isobutyl acetate
Become, then use distillation to carry out processing and obtaining；Described method comprises the steps:
1) preparation of the alumina support described in:
Add a certain amount of deionized water in a kettle. and acetic acid that isobutyl acetate obtains containing 0.1-10wt% is different
The butyl ester aqueous solution, is heated to 50-95 DEG C under mechanical agitation, after addition polyethylene glycol stirs, and flow addition
Al2O3 content is sodium aluminate solution and the salpeter solution of 10-30wt% of 100-200g/L, and the reaction time controls
At 0.5-1 hour, after reaction terminates, regulating reaction solution with ammoniacal liquor is 7-10 in pH value, synthermal continuation
Stirring reaction solution filtered after 0.5-1 hour, uses absolute ethanol washing filter cake again, add after deionized water washing
After isobutyl acetate, high shear homogenous disperse mulser is used to distill after stirring, until not having liquid
Cut steams, and cooling is taken out, and 150 DEG C obtain alumina support powder in dry 3-8 hour；Wherein said poly-second
The weight of glycol is the 0.5wt%-1wt% of deionized water weight, described isobutyl acetate and the body of deionized water
Long-pending ratio is 0.5-1；
2) preparation of oil hydrogenation catalyst presoma
The aqueous solution of the preparation isobutyl acetate containing 0.1-10wt% adds reactor as end water, unlatching stirring
And heat, be warming up to 60-95 DEG C, add after polyethylene glycol stirs, by prepare in advance containing zirconium, magnesium
Or the nickel salt acid solution of iron auxiliary agent and alkaline solution stream join in end water, after completion of the reaction, oxidation is added
Alumina supporter powder, with ammoniacal liquor regulation reaction solution between pH value 7-10, continues stirring 0.5-1.5 hour,
Filtering, filter with absolute ethanol washing after the washing of filter cake deionized water again, the acetic acid adding 500-1000mL is different
After butyl ester, high shear homogenous disperse mulser is used to distill after stirring, until not having liquid distillate to steam
Going out, cooling is taken out, and 150 DEG C obtain the oil hydrogenation catalyst precursor powder loosened for dry 3-8 hour；Its
Described in the 0.5wt%-1wt% that weight is deionized water weight of polyethylene glycol, described isobutyl acetate with go
The volume ratio of ionized water is 0.5-1；
3) oil hydrogenation catalyst presoma reduction
Be passed through nitrogen at keeping 450 DEG C after being calcined 3-5 hour by 400-600 DEG C of dried powder, hydrogen mixes
Closing gas reduction, cooling, nitrogen protection obtains finished catalyst.
According to said method of the present invention, preparing the nickeliferous acid solution of oil hydrogenation catalyst is nitric acid
The one of the solution of nickel, nickel chloride, nickel sulfate, nickel acetate, nickel formate, nickel oxalate and deionized water preparation or
Several.
According to said method of the present invention, preparing oil hydrogenation catalyst alkaline solution is sodium carbonate, carbonic acid
One or more of the solution that hydrogen sodium, NaOH, sodium oxalate, sodium acetate are prepared with deionized water.
The inventive method have employed is prepared catalyst load by the mixed liquor oil-water media system of isobutyl acetate Yu water
Body and catalyst precursor, then prepare catalyst through distillation process, prepared catalyst grain size is uniform, reaction is lived
Property high；Additionally, the catalyst dispersity that the present invention prepares can be superior, after drying without grinding, decrease preparation
Operation, reduces labour intensity, superior to consaturated oil hydrogenation reactivity worth.
Detailed description of the invention
Embodiment 1
The isobutyl acetate adding 1L deionized water and 100g in a kettle. obtains i-butyl aqueous solution of ester,
It is heated to 75 DEG C under mechanical agitation, after the polyethylene glycol 2000 of addition 5g stirs, and flows addition 250mL
Sodium aluminate solution (Al2O3Content is 200g/L) and the salpeter solution 300mL of 30wt%, the reaction time controls
0.75 hour, after reaction terminates, be 8 by ammoniacal liquor regulation reaction solution to pH value, and synthermal aging reaction is molten
Liquid filters for 0.75 hour, uses absolute ethanol washing filter cake again, add 500mL acetic acid different after deionized water washing
Butyl ester employing high shear homogenous disperse mulser is poured round-bottomed flask into after stirring and is distilled, until not having liquid
Body cut steams, and cooling is taken out, and 150 DEG C of drying obtain alumina support powder.
Weigh 60g solid nitric acid nickel (Ni (NO3)2·6H2O) it is placed in beaker, adds 500g deionized water, stirring
It is allowed to be completely dissolved and be configured to the nickel nitrate solution of 6.7wt%.
16g zirconium nitrate (Zr (NO is added in nickel nitrate solution3)4·5H2O), stirring makes it fully dissolve.
Weigh 30g solid sodium carbonate (Na2CO3) be placed in beaker, adding 500g deionized water, stirring is allowed to
It is completely dissolved and is configured to the sodium carbonate liquor of 5.7wt%.
Reactor adds 1L deionized water and 100g isobutyl acetate, opens and be stirred and heated to 80 DEG C,
Add after 5g polyethylene glycol 2000 and flow the nickel nitrate solution and sodium carbonate liquor added containing zirconium, when controlling reaction
Between 1 hour, after reaction solution all adds, with ammonia spirit regulation reacting solution pH value to 8, add system
Standby alumina support, synthermal continuation is stirred 1 hour and is filtered, is washed with deionized filter cake, then uses
Add 1000mL isobutyl acetate after ethanol washing filter cake, use high shear homogenous disperse mulser to stir
After pour round-bottomed flask into and distill, until not having liquid distillate to steam, cooling is taken out, and 150 DEG C of drying obtain
Catalyst precursor powder.
Take catalyst precursor powder and load reduction reactor, be warming up to latter 3 hours of 450 DEG C of calcinings synthermal logical
Entering nitrogen and hydrogen gas mixture reduces 5 hours, cooling nitrogen protection prepares oil hydrogenation catalyst.
Weigh 1000g tallow oil (iodine number is 36.12) and the catalyst of nickeliferous 0.5g, pour autoclave into,
Opening stirring, be warming up to 185 DEG C, be passed through hydrogen, keeping reactor pressure is that 1.5MPa carries out oil hydrogenation
Reaction.Hydrogenation reaction is carried out 2 hours, sampling analysis measuring different time sections hydrogenation tallow oil iodine number during this period.
Control reference sample is the similar industrial catalyst typical sample used in the market, and the catalyst of use is nickeliferous
Measure with to prepare sample suitable.Test result is shown in Table 1.
Table 1
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 1 sample iodine number | 36.12 | 21.78 | 10.96 | 3.62 | 2.13 |
Embodiment 2
The isobutyl acetate adding 1L deionized water and 10g in a kettle. obtains i-butyl aqueous solution of ester,
It is heated to 85 DEG C under mechanical agitation, after the polyethylene glycol 2000 of addition 5g stirs, and flows addition 500mL
Sodium aluminate solution (Al2O3Content is 100g/L) and the salpeter solution 600mL of 15wt%, the reaction time controls 1
Hour, after reaction terminates, it is 8 by ammoniacal liquor regulation reaction solution to pH value, synthermal aging reaction solution 0.75
Hour filter, use absolute ethanol washing filter cake again after deionized water washing, after addition 500mL isobutyl acetate
Use high shear homogenous disperse mulser to pour round-bottomed flask into after stirring to distill, until not having liquid to evaporate
Dividing and steam, cooling is taken out, and 150 DEG C of drying obtain alumina support powder.
Weigh 60g solid nitric acid nickel (Ni (NO3)2·6H2O), 5g zirconium nitrate (Zr (NO3)4·5H2O), 0.8g nitric acid
Iron (Fe (NO3)3·9H2O).Prepare the nickel nitrate solution of iron content as described in Example 1.
Weigh 25g solid sodium carbonate (Na2CO3), prepare sodium carbonate liquor as described in Example 1.
Reactor adds 1L deionized water and 100g isobutyl acetate, opens and be stirred and heated to 95 DEG C,
Add after 10g Macrogol 4000 and flow addition containing zirconium, the nickel nitrate solution of iron and sodium carbonate liquor, controlling
1 hour reaction time, after reaction solution all adds, with ammonia spirit regulation reacting solution pH value to 9,
Add the alumina support of preparation, continue aging 1 hour to filter, be washed with deionized filter cake, then use
Add 1000mL isobutyl acetate after ethanol washing filter cake, use high shear homogenous disperse mulser to stir
After pour round-bottomed flask into and distill, until not having liquid distillate to steam, cooling is taken out 150 DEG C of drying and is urged
Agent precursor powder.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, tallow oil hydroconversion condition are with real
Executing example 1, after hydrogenation, the iodine number of tallow oil is as shown in table 2:
Table 2
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 2 sample iodine number | 36.12 | 23.57 | 12.11 | 4.34 | 1.51 |
Embodiment 3
Add in a kettle. under 1L deionized water and the isobutyl acetate of 5g, mechanical agitation and be heated to 75 DEG C,
After the Macrogol 4000 of addition 5g stirs, and flow addition 500mL sodium aluminate solution (Al2O3Content is
100g/L) and the salpeter solution 600mL of 15wt%, the reaction time controls at 1 hour, after reaction terminates, uses
Ammoniacal liquor regulation reaction solution to pH value is 7, and synthermal aging reaction solution filters for 0.75 hour, deionized water
Use absolute ethanol washing filter cake after washing again, after adding 500mL isobutyl acetate, use high shear homogenous disperse
Mulser is poured round-bottomed flask into after stirring and is distilled, until not having liquid distillate to steam, cooling is taken out,
150 DEG C of drying obtain alumina support powder.
Weigh 60g solid nitric acid nickel (Ni (NO3)2·6H2O), 0.2g zirconium nitrate (Zr (NO3)4·5H2O), 0.32g
Magnesium nitrate (Mg (NO3)2·6H2O).Preparation is containing zirconium, the nickel nitrate solution of magnesium as described in Example 1.
Weigh 23g solid sodium carbonate (Na2CO3).Prepare the sodium carbonate liquor of iron content as described in Example 1.
Reactor adds 1L deionized water and 5g isobutyl acetate, opens and be stirred and heated to 75 DEG C, add
After entering 5g Macrogol 4000 and flow addition containing zirconium, the nickel nitrate solution of magnesium and sodium carbonate liquor, control reaction
1 hour time, after reaction solution all adds, with ammonia spirit regulation reacting solution pH value to 9, add
The alumina support of preparation, continues aging 1 hour to filter, is washed with deionized filter cake, then uses ethanol
Add 1000mL isobutyl acetate after washing filter cake, use high shear homogenous disperse mulser to fall after stirring
Entering round-bottomed flask to distill, until not having liquid distillate to steam, cooling is taken out, and 150 DEG C of drying are catalyzed
Agent precursor powder.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, tallow oil hydroconversion condition are with real
Executing example 1, after hydrogenation, the iodine number of tallow oil is as shown in table 3:
Table 3
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 3 sample iodine number | 36.12 | 16.13 | 7.36 | 1.75 | 1.12 |
Embodiment 4
Add in a kettle. under 1L deionized water and the isobutyl acetate of 50g, mechanical agitation and be heated to 85 DEG C,
After the Macrogol 4000 of addition 10g stirs, and flow addition 250mL sodium aluminate solution (Al2O3Content is
200g/L) and the salpeter solution 300mL of 30wt%, the reaction time controls at 1 hour, after reaction terminates, uses
Ammoniacal liquor regulation reaction solution to pH value is 8, and synthermal aging reaction solution filters for 0.75 hour, deionized water
Use absolute ethanol washing filter cake after washing again, after adding 500mL isobutyl acetate, use high shear homogenous disperse
Mulser is poured round-bottomed flask into after stirring and is distilled, until not having liquid distillate to steam, cooling is taken out,
150 DEG C of drying obtain alumina support powder.
Weigh 60g solid nitric acid nickel (Ni (NO3)2·6H2O), 16g zirconium nitrate (Zr (NO3)4·5H2O).Press
The method preparation of embodiment 1 nickel nitrate solution containing zirconium.
Weigh 30g solid sodium carbonate (Na2CO3).Prepare sodium carbonate liquor as described in Example 1.
Reactor adds 1L deionized water and 50g isobutyl acetate, opens and be stirred and heated to 85 DEG C, add
After entering 10g Macrogol 4000 and flow and add containing the nickel nitrate solution of zirconium and sodium carbonate liquor, when controlling reaction
Between 1 hour, after reaction solution all adds, with ammonia spirit regulation reacting solution pH value to 9, add system
Standby alumina support, continues aging 1 hour to filter, is washed with deionized filter cake, then washes with ethanol
Add 1000mL isobutyl acetate after washing filter cake, use high shear homogenous disperse mulser to pour into after stirring
Round-bottomed flask distills, until not having liquid distillate to steam, cooling is taken out, and 150 DEG C of drying obtain catalyst
Precursor powder.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, tallow oil hydroconversion condition are with real
Executing example 1, after hydrogenation, the iodine number of tallow oil is as shown in table 4:
Table 4
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 4 sample iodine number | 36.12 | 19.76 | 10.31 | 3.48 | 1.59 |
Embodiment 5
Add in a kettle. under 1L deionized water and the isobutyl acetate of 10g, mechanical agitation and be heated to 75 DEG C,
After the Macrogol 4000 of addition 5g stirs, and flow addition 250mL sodium aluminate solution (Al2O3Content is
200g/L) and the salpeter solution 300mL of 30wt%, the reaction time controls at 1 hour, after reaction terminates, uses
Ammoniacal liquor regulation reaction solution to pH value is 7, and synthermal aging reaction solution filters for 0.75 hour, deionized water
Use absolute ethanol washing filter cake after washing again, after adding 500mL isobutyl acetate, use high shear homogenous disperse
Mulser is poured round-bottomed flask into after stirring and is distilled, until not having liquid distillate to steam, cooling is taken out,
150 DEG C of drying obtain alumina support powder.
Weigh 60g solid nitric acid nickel (Ni (NO3)2·6H2O), 0.2g zirconium nitrate (Zr (NO3)4·5H2O), 0.5g
Ferric nitrate (Fe (NO3)3·9H2O).Preparation is containing zirconium, the nickel nitrate solution of iron as described in Example 1.
Weigh 17g solid sodium hydroxide (NaOH), prepare sodium carbonate liquor as described in Example 1.
Reactor adds 1L deionized water and 10g isobutyl acetate, opens and be stirred and heated to 85 DEG C, add
After entering 5g Macrogol 4000 and flow addition containing zirconium, the nickel nitrate solution of iron and sodium hydroxide solution, control anti-
Between Ying Shi 1 hour, after reaction solution all adds, with ammonia spirit regulation reacting solution pH value to 7, add
Enter the alumina support of preparation, continue aging 1 hour to filter, be washed with deionized filter cake, then use second
1000mL isobutyl acetate is added, after using high shear homogenous disperse mulser to stir after alcohol washing filter cake
Pouring round-bottomed flask into distill, until not having liquid distillate to steam, cooling is taken out, and 150 DEG C of drying are urged
Agent precursor powder.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, tallow oil hydroconversion condition are with real
Executing example 1, after hydrogenation, the iodine number of tallow oil is as shown in table 5:
Table 5
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 5 sample iodine number | 36.12 | 16.57 | 8.25 | 2.18 | 1.43 |
Embodiment 6
The isobutyl acetate adding 1L deionized water and 5g in a kettle. obtains i-butyl aqueous solution of ester, machine
It is heated to 85 DEG C under tool stirring, after the Macrogol 4000 of addition 5g stirs, and flows addition 500mL aluminium
Acid sodium solution (Al2O3Content is 100g/L) and the salpeter solution 600mL of 15wt%, the reaction time controls 1
Hour, after reaction terminates, with ammoniacal liquor regulation reacting solution pH value to 7, synthermal aging reaction solution 0.75
Hour filter, use absolute ethanol washing filter cake again after deionized water washing, after addition 500mL isobutyl acetate
Use high shear homogenous disperse mulser to pour round-bottomed flask into after stirring to distill, until not having liquid to evaporate
Dividing and steam, cooling is taken out, and 150 DEG C of drying obtain alumina support powder.
Weigh 54g solid sulphuric acid nickel (NiSO4·6H2O), 0.2g zirconium nitrate (Zr (NO3)4·5H2O), 0.5g nitre
Acid magnesium (Mg (NO3)2·6H2O).Preparation is containing zirconium, the nickel nitrate solution of magnesium as described in Example 1.
Weigh 22g solid sodium carbonate (Na2CO3), preparation sodium carbonate nickel nitrate solution as described in Example 1.
Reactor adds 1L deionized water and 5g isobutyl acetate, opens and be stirred and heated to 85 DEG C, add
After entering 5g Macrogol 4000 and flow addition containing zirconium, the nickel nitrate solution of magnesium and sodium carbonate liquor, control reaction
1 hour time, after reaction solution all adds, with ammonia spirit regulation reacting solution pH value to 8, add
The alumina support of preparation, continues aging 1 hour to filter, is washed with deionized filter cake, then uses ethanol
Add 1000mL isobutyl acetate after washing filter cake, use high shear homogenous disperse mulser to fall after stirring
Entering round-bottomed flask to distill, until not having liquid distillate to steam, cooling is taken out, and 150 DEG C of drying are catalyzed
Agent precursor powder.
The reduction experiment of catalyst precarsor is identical with embodiment 1, and catalyst amount, tallow oil hydroconversion condition are with real
Executing example 1, after hydrogenation, the iodine number of tallow oil is as shown in table 4:
Table 6
| Reaction time (hr) | 0 | 0.5 | 1 | 1.5 | 2 |
| Reference sample iodine number | 36.12 | 17.65 | 9.34 | 2.34 | 1.65 |
| Embodiment 6 sample iodine number | 36.12 | 16.37 | 8.56 | 2.05 | 1.31 |
Claims (3)
1. the method that an organic-aqueous system prepares oil hydrogenation catalyst, it is characterised in that
Described catalyst is with aluminum oxide as carrier, and nickel is active component, and zirconium, magnesium or iron are auxiliary agent；Each group
Divide and account for overall catalyst weight meter, nickel 10-30wt%, alumina support 50-85wt%, auxiliary agent zirconium, magnesium or iron
0.01-10wt%, described alumina support specific surface area is 120-450m2/ g, pore volume is 1-2.7m3/g；Its
Described in alumina support and catalyst precursor be all to synthesize in the aqueous solution of isobutyl acetate, then
Distillation is used to carry out processing and obtaining；Described method comprises the steps:
1) preparation of the alumina support described in:
Add a certain amount of deionized water in a kettle. and acetic acid that isobutyl acetate obtains containing 0.1-10wt% is different
The butyl ester aqueous solution, is heated to 50-95 DEG C under mechanical agitation, after addition polyethylene glycol stirs, and flow addition
Al2O3Content is sodium aluminate solution and the salpeter solution of 10-30wt% of 100-200g/L, and the reaction time controls
At 0.5-1 hour, after reaction terminates, regulating reaction solution with ammoniacal liquor is 7-10 in pH value, synthermal continuation
Stirring reaction solution filtered after 0.5-1 hour, uses absolute ethanol washing filter cake again, add after deionized water washing
After isobutyl acetate, high shear homogenous disperse mulser is used to distill after stirring, until not having liquid
Cut steams, and cooling is taken out, and 150 DEG C obtain alumina support powder in dry 3-8 hour；Wherein said poly-second
The weight of glycol is the 0.5wt%-1wt% of deionized water weight, described isobutyl acetate and the body of deionized water
Long-pending ratio is 0.5-1；
2) preparation of oil hydrogenation catalyst presoma
The aqueous solution of the preparation isobutyl acetate containing 0.1-10wt% adds reactor as end water, unlatching stirring
And heat, it is warming up to 60-95 DEG C, on the basis of amount of deionized water, adds 0.5-1% polyethylene glycol and stir
After, the nickeliferous acid solution containing zirconium, magnesium or iron auxiliary agent prepared in advance and alkaline solution stream are joined
In end water, after completion of the reaction, add alumina support powder, with ammoniacal liquor regulation reaction solution in pH value 7-10
Between, continue stirring 0.5-1.5 hour, filter, after the washing of filter cake deionized water, use absolute ethanol washing mistake again
Filter, after adding the isobutyl acetate of 500-1000mL, after using high shear homogenous disperse mulser to stir
Distilling, until do not have liquid distillate to steam, cooling is taken out, and 150 DEG C obtain loosening for dry 3-8 hour
Oil hydrogenation catalyst precursor powder；The weight of wherein said polyethylene glycol is the 0.5 of deionized water weight
Wt%-1wt%, described isobutyl acetate is 0.5-1 with the volume ratio of deionized water；
3) oil hydrogenation catalyst presoma reduction
Be passed through nitrogen at keeping 450 DEG C after being calcined 3-5 hour by 400-600 DEG C of dried powder, hydrogen mixes
Closing gas reduction, cooling, nitrogen protection obtains finished catalyst.
The most in accordance with the method for claim 1, it is characterised in that prepare the acidity that oil hydrogenation catalyst is nickeliferous
Solution is that nickel nitrate, nickel chloride, nickel sulfate, nickel acetate, nickel formate, nickel oxalate are molten with what deionized water was prepared
One or more of liquid.
The most in accordance with the method for claim 1, it is characterised in that preparing oil hydrogenation catalyst alkaline solution is
The one of the solution of sodium carbonate, sodium acid carbonate, NaOH, sodium oxalate, sodium acetate and deionized water preparation or
Several.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410643222.5A CN104399467B (en) | 2014-11-10 | 2014-11-10 | A kind of method preparing oil hydrogenation catalyst at organic-aqueous system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410643222.5A CN104399467B (en) | 2014-11-10 | 2014-11-10 | A kind of method preparing oil hydrogenation catalyst at organic-aqueous system |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104399467A CN104399467A (en) | 2015-03-11 |
| CN104399467B true CN104399467B (en) | 2016-08-24 |
Family
ID=52637171
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410643222.5A Active CN104399467B (en) | 2014-11-10 | 2014-11-10 | A kind of method preparing oil hydrogenation catalyst at organic-aqueous system |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104399467B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106076359A (en) * | 2016-07-14 | 2016-11-09 | 安徽海德石油化工有限公司 | A kind of oil hydrogenation deoxidation nickel-base catalyst |
| CN112691669A (en) * | 2019-10-23 | 2021-04-23 | 中国石油化工股份有限公司 | Ni/NiO nano catalyst and preparation method and application thereof |
| CN113070058B (en) * | 2021-03-04 | 2023-02-28 | 青岛创启新能催化科技有限公司 | Composite carrier single-atom catalyst for organic hydrogen storage medium dehydrogenation and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1132966A (en) * | 1979-12-12 | 1982-10-05 | John Torok | Supported nickel catalysts and process for their preparation |
| CN102872876B (en) * | 2012-10-15 | 2014-11-05 | 中国海洋石油总公司 | Preparation method of grease hydrogenation catalyst |
| CN102989462B (en) * | 2012-10-24 | 2014-06-04 | 中国海洋石油总公司 | Method for preparing oils and fats hydrogenation catalyst with high activity |
| CN102949996A (en) * | 2012-10-26 | 2013-03-06 | 中国海洋石油总公司 | Preparation method of unsaturated fat nickel hydrogenation catalyst |
| CN103521230B (en) * | 2013-10-11 | 2015-06-24 | 中国海洋石油总公司 | Preparation method of unsaturated fat hydrogenation catalyst |
-
2014
- 2014-11-10 CN CN201410643222.5A patent/CN104399467B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104399467A (en) | 2015-03-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104399467B (en) | A kind of method preparing oil hydrogenation catalyst at organic-aqueous system | |
| CN106732564B (en) | Aromatic hydrogenation rhodium/activated-carbon catalyst preparation method and application | |
| CN105498756B (en) | The catalyst of hydrogenation of carbon dioxide methanol | |
| CN104645981B (en) | Pyrolysis gasoline hydrogenation catalyst and preparation method thereof | |
| CN106179381B (en) | The preparation method of Hydrobon catalyst | |
| CN105985208A (en) | Application of supported gold cluster catalyst | |
| CN106423200A (en) | Fluidized laver hydrogen appending catalyst and preparation method thereof | |
| CN107011194A (en) | A kind of method that hydramine and diamines are prepared by glycolaldehyde reduction amination | |
| CN105540685B (en) | Method for preparing tetraammineplatinum hydrogen carbonate | |
| CN106582634A (en) | Highly active ruthenium-carbon catalyst modified by transition metal atoms and preparation method thereof | |
| CN106187737A (en) | A kind of method of carbon-supported polynary noble metal catalyst catalytic oxidation of glucose preparation of gluconic acid sodium | |
| JPH03207449A (en) | Nickel/silica catalyst and its manufacture | |
| CN107899581A (en) | One kind is carried on SiO2The preparation method and applications of Raney nickel on microballoon | |
| CN102872876B (en) | Preparation method of grease hydrogenation catalyst | |
| CN106582709A (en) | Catalyst for synthesizing primary aromatic amine by virtue of hydrogenation of aromatic nitrile and preparation method of catalyst | |
| CN108067213A (en) | It is a kind of for catalyst of aniline rectification residue recycling and preparation method thereof | |
| CN106179385B (en) | A kind of preparation method of Hydrobon catalyst | |
| CN105363460B (en) | A kind of non-loading type deep hydrogenation catalyst and preparation method thereof | |
| CN105688877B (en) | Iron-based catalyst for Fischer-Tropsch synthesis and preparation method thereof | |
| CN106179388B (en) | A kind of preparation method of hydrotreating catalyst | |
| CN108863706A (en) | A kind of selection method of hydrotreating of the C-4-fraction containing alkynes | |
| CN106861766A (en) | A kind of alumina support and preparation method and application | |
| CN106905266B (en) | A kind of method that epoxidation of styrene prepares Styryl oxide | |
| CN106179382B (en) | A kind of preparation method of body phase hydrotreating catalyst | |
| CN106540705A (en) | A kind of preparation method of silica supported Ni-based oil hydrogenation catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Applicant after: CNOOC Energy Development Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Tianjin Chemical Research & Design Institute Applicant before: CNOOC Energy Development Co., Ltd. |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20161012 Address after: No. three road 300131 Tianjin city Hongqiao District dingzigu No. 85 Patentee after: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Patentee after: CNOOC Energy Development Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Patentee before: China National Offshore Oil Corporation Patentee before: CNOOC TIANJIN CHEMICAL RESEARCH & DESIGN INSTITUTE CO., LTD. Patentee before: CNOOC Energy Development Co., Ltd. |