CN104513135B - A kind of method that decenal liquid-phase hydrogenatin prepares decyl alcohol - Google Patents
A kind of method that decenal liquid-phase hydrogenatin prepares decyl alcohol Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/175—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of an oxo group
Abstract
The invention discloses a kind of method that decenal liquid-phase hydrogenatin prepares decyl alcohol, first step hydrogenation is carried out using at least one liquid phase hydrogenation reactor on the first catalyst, the first described catalyst is oxide carried Ni systems or Cu series catalysts, second step hydrogenation is carried out using at least one liquid phase hydrogenation reactor on the second catalyst, and the second described catalyst is thunder Buddhist nun's Ni catalyst of organic polymer load.The hydrogenated products residual olefine aldehydr that the two steps hydrogenation that the present invention is used is obtained is few, and good product quality, product yield is high.
Description
Technical field
The invention belongs to catalytic hydrogenation field, relate in particular to a kind of by side of the decenal two-step method Hydrogenation for decyl alcohol
Method.
Background technology
The synthesis of current plasticizer mainly uses octyl alconyl, due to environmental protection and the requirement in terms of safety, it has been suggested that and open
Begin one of to be exactly and to have put into industrialized production using the alcohol production plasticizer of higher carbon number, decyl alcohol.Decyl alcohol boiling point compares octanol
Height, the plasticizer volatility being made is lower, is conducive to environmental protection and health, is paid close attention to both at home and abroad in recent years.2- third
Base enanthol is one of important representative of decyl alcohol.The route of production decyl alcohol mainly has：（1）Pass through the trimerization or propylene of propylene and butylene
Oligomeric cutting, obtains C9 alkene, then by carbonylation synthesis, hydrogenation, generates isodecanol；（2）Butene hydroformylation synthesis penta
Aldehyde, then through condensation generation decenal, repeated hydrogenation generation decyl alcohol.
Aldehyde hydrogenation technique is divided to two kinds of vapor phase method and liquid phase method.Adding hydrogen to aldehyde in gas phase technique, poor product quality, reactor volume
Greatly, consume energy high, and load does not reach design requirement, liquid-phase hydrogenatin technique is using cryogenic high pressure therefore can overcome the shortcoming of vapor phase method.
But for the production of higher alcohols, if liquid-phase hydrogenatin is not exclusively, the olefine aldehydr of residual can influence the quality of product.
Patent CN101185893A proposes a kind of catalyst and its preparation side for decenal gas phase hydrogenation isodecanol
Method, catalyst is prepared using coprecipitation, and containing cupric oxide, zinc oxide, aluminum oxide, coagent adds for decenal gas phase
Hydrogen isodecanol, with higher decenal conversion ratio and isodecanol selectivity.
Patent CN102666455A propositions are a kind of to prepare the side of at least one decyl alcohol by hydrogenating at least one decenal
Method.Using at least two reactors, wherein first reactor uses copper system and/or nickel catalyst, and second reactor uses palladium
Or ruthenium catalyst, all it is to be carried out in the liquid phase on solid catalyst.Can be with high yield hydrogen according to the inventive method decenal
Decyl alcohol is melted into, the content of the unsaturated decenal in hydrogenation discharging is less than 1500ppm.The method for hydrogenation of the invention is more multiple
It is miscellaneous, connected using multiple reactors, and also second reactor uses expensive noble metal catalyst.
At present, there is contradiction in the activity and selectivity of liquid phase hydrogenating catalyst, and particularly selectivity is difficult to maintain normally
Level, accessory substance is more, and problem is brought to production, and in order that product is qualified, it is necessary to which expending a large amount of steam carries out impurity separation.
For capraldehyde Hydrogenation reacting, it is necessary to have the hydrogenation catalyst of high activity and high selectivity simultaneously for decyl alcohol.
The content of the invention
Object of the present invention is to provide a kind of method of decenal Hydrogenation for decyl alcohol, this method is different from traditional
Liquid phase aldehyde method of hydrotreating, solves the problem of hydrogenation depth present in conventional method is inadequate, accessory substance is more.
The invention discloses a kind of method that decenal liquid-phase hydrogenatin prepares decyl alcohol, first step hydrogenation uses at least one liquid
Phase hydrogenation reactor is carried out on the first catalyst, and the first described catalyst is oxide carried Ni systems or the catalysis of Cu systems
Agent, second step hydrogenation is carried out using at least one liquid phase hydrogenation reactor on the second catalyst, and the second described catalyst is
Thunder Buddhist nun's Ni catalyst of organic polymer load.
Reactant first passes through the first step and is hydrogenated with, then by second step deep hydrogenation, obtains the good alcohol of product colourity,
And target product selectivity is good, product yield is high.
The Ni catalyst that described first step hydrogenation is used, can make for aluminum oxide, silica, molecular sieve, activated carbon etc.
For the Ni catalyst of carrier；The Cu catalyst used, generally the compound of zinc oxide, aluminum oxide and cupric oxide or
The copper catalyst of other inorganic carriers load.
First step hydroprocessing scheme：Hydrogenation reaction temperature is 50 DEG C -200 DEG C, and reaction pressure is 0.5-8.0MPa, reaction
Air speed is 0.05-5.0h-1（With the liquid volume metering of aldehyde）, hydrogen is 200~10000 with aldehyde volume ratio:1.
The first step is hydrogenated with preferred operation scheme：Hydrogenation reaction temperature is 90 DEG C -150 DEG C, and reaction pressure is 3.0-
5.0MPa, reaction aldehyde air speed is 0.1-2.0h-1（With the liquid volume metering of aldehyde）, hydrogen is 600~2000 with aldehyde volume ratio:1.
The thunder Buddhist nun's Ni catalyst for the organic polymer load that described second step hydrogenation is used, it includes：Organic polymer
Material support, the Raney alloy particle for being supported on organic polymer carrier surface, wherein described Raney alloy particle fraction is embedding
Enter in high-molecular organic material carrier.
Second step hydroprocessing scheme：Hydrogenation reaction temperature is 50 DEG C -200 DEG C, and reaction pressure is 0.5-8.0MPa, reaction
Air speed is 0.05-5.0h-1（With the liquid volume metering of aldehyde）, hydrogen is 200~10000 with aldehyde volume ratio:1.
Second step is hydrogenated with preferred operation scheme：Hydrogenation reaction temperature is 90 DEG C -150 DEG C, and reaction pressure is 3.0-
5.0MPa, reaction aldehyde air speed is 0.1-2.0h-1（With the liquid volume metering of aldehyde）, hydrogen is 600~2000 with aldehyde volume ratio:1.
Thunder Buddhist nun's Ni catalyst of described high-molecular organic material load, " Raney alloy particle fraction is embedded in organic high score
In sub- material support " refer in some insertion carrier of each Raney alloy particle.Described Raney alloy is nickel aluminium
Alloy, nickel silicon alloy etc..In order to improve catalyst activity or selectivity, Raney alloy may be incorporated into accelerator, accelerator
Selected from least one of Mo, Cr, Ti, Fe, Pt, Pd, Rh, Ru, the Raney alloy of multicomponent mixture is formed, the amount of accelerator is thunder
0.01~5wt% of damping alloy total amount.
It is by carrier processing and forming temperature that described Raney alloy particle fraction, which is embedded in organic polymeric carrier material,
Under the conditions of degree or under conditions of uncured sizing, it is molded what the carrier coated by Raney alloy particle reached.In heat and pressure
Under double action, high-molecular organic material carrier is produced in softening transform, the carrier that Raney alloy particle is softened by part press-in,
While particle fraction is pressed into, the carrier of softening can be overflowed in particle periphery, and the carrier of spilling, which is not only acted as, to be firmly fixed
The effect of particle, and other particles can be pressed into again on the carrier surface of spilling, so repeatedly, make Raney alloy particle fraction
Press-in is possible in the carrier surface of press-in.As described above, the present invention efficiently utilizes overall surface area so that catalysis
The active metallic content of agent load is very high.Further, since in Raney alloy particle fraction insertion carrier, the carrier of particle periphery is made
To firmly fix thing, make catalyst that there is good stability.
The preferred plastics of described high-molecular organic material or its modified product, plastics include thermosetting plastics and thermoplasticity is moulded
Material.Specific plastics include：Polyolefin, poly(4-methyl-1-pentene), polyamide（As nylon -5, Nylon-12, nylon-6/6,
Nylon-6/10, nylon-11）, polycarbonate resin, homopolymerization and/or copolymerized methanal, monounsaturated dicarboxylic acid and dihydric alcohol pass through polycondensation
Reaction obtained linear polyester, aromatic ring macromolecule（Aromatic ring macromolecule is the polymer that molecule is only made up of aromatic ring and linking group,
Such as polyphenyl, polyphenylene oxide, polyphenylene sulfide, polyarylsulfone (PAS), poly aryl ketone.Aromatic polyester, aromatic polyamides）, heterocyclic polymer（Heterocycle high score
Son is the high polymer material for also having heterocycle on molecular backbone in addition to aromatic ring, such as polybenzimidazoles）, fluoropolymer, acrylic acid series
Resin, mephenesin Carbamate, epoxy resin, phenolic resin, Lauxite, melamine resin etc..It is preferred polyolefm resin, poly-
At least one of amide resin, polystyrene, epoxy resin and phenolic resin, more preferably polypropylene, nylon-6, nylon -66,
At least one of polystyrene, phenolic resin and epoxy resin.
Modifying plastics product refers to the modified product obtained using existing modifying plastics method.Modifying plastics method includes
But it is not limited to following methods：The graft modification of polarity or non-polar monomer or its polymer；By with inorganic or organic enhancing
Melt blending modifications of material such as material, toughening material, the firm material of increasing, increase heat-resisting material etc..
The preparation method of thunder Buddhist nun's Ni catalyst of organic polymer load of the present invention includes：In organic polymer material
Expect under processing and forming temperature conditionss or under conditions of uncured sizing, to be molded the organic polymer material coated by Raney alloy particle
Material.
For different high-molecular organic material carriers, specific preparation method is slightly different.
When carrier uses organic thermoplastic polymer material, can specifically it select with the following method（ⅰ）Or（ⅱ）Prepare：
Method（ⅰ）：
（1）Thermoplastic carrier is processed into any shape of size needed for meeting fixed bed catalyst or fluid catalyst
The particle of shape；
（2）Above-mentioned carrier granular is placed in Raney alloy particle, i.e., carrier is coated by Raney alloy particle completely；
（3）Under corresponding thermoplastic carrier's processing and forming temperature conditionss, molding is placed in thermoplasticity in Raney alloy particle
Carrier, Raney alloy particle fraction is pressed into thermoplastic carrier's particle so that Raney alloy particle is supported on thermoplastic carrier
Particle surface is simultaneously partially submerged into carrier, is cooled down, and sieving obtains granular loaded catalyst.
The particle size of particulate supported type catalyst is can meet fixed bed catalyst or fluid catalyst institute
On the basis of needing particle size.The shape of particle can be any irregular shape, orbicule, hemispherical mass, cylinder, semicircle
The combination of column, prism-shaped body, cube, cuboid, ring bodies, half-annuli, hollow cylinder, tooth form or more shape
Deng the combination of preferably spherical, annular, tooth form, cylinder or more shape.Thermoplastic carrier's particle can by raw material processing into
Type, can also directly use the thermoplastic carrier's particle being molded purchased in market.
Or method（ⅱ）：
（1）The sheet material of thickness needed for thermoplastic carrier is processed into fixed bed catalyst or fluid catalyst；
（2）Raney alloy uniform particle is coated to the surface of resulting vehicle sheet material；
（3）Under the conventional processing and forming temperature conditionss of corresponding thermoplastic carrier, to the piece coated by Raney alloy particle
Material is molded, and Raney alloy particle is used any available process equipment, passed through by part press-in support sheet after cooling
Cutting, cut, the support sheet that area load has Raney alloy particle is processed into required shape by punching press or the method such as broken
The particle of shape and size, finally also obtains granular loaded catalyst.
Method（ⅰ）Or method（ⅱ）Described in thermoplastic carrier can add such as antioxidant, help antioxidant, heat steady
Determine agent, light stabilizer, ozone stabilizers, processing aid, plasticizer, softening agent, anti-blocking agent, foaming agent, dyestuff, pigment, wax,
The auxiliary agent commonly used in the plastic processes such as extender, organic acid, fire retardant and coupling agent.Adjuvant used consumption is routine
Consumption, or be adjusted according to the requirement of actual conditions.
When carrier uses thermosetting high-molecular organic material carrier, can specifically it select with the following method（ⅲ）Or（ⅳ）System
It is standby：
Method（ⅲ）：
（1）Suitable curing system is configured to according to the conventional curing formula of thermoset carrier, liquid system can be stirred directly
Mix uniform；Pulverized solid system can directly be blended uniformly；The available any disintegrating apparatus industrially commonly used of granulated solid system
It is blended after crushing uniform.
（2）Any cavity shape of particle size needed for it can meet fixed bed catalyst or fluid catalyst
Raney alloy powder is first added in mould, the uncured thermosetting high-molecular organic material prepared is added, then adds
Raney alloy powder, carries out partially cured sizing under conventional condition of cure, is then coated with thunder Buddhist nun to partially cured sizing
The pelleted substrate of alloyed powder proceeds molded curing, completion of cure with any available high-molecular organic material process equipment
Afterwards, sieve, that is, obtain particulate supported type catalyst；
Or method（ⅳ）：
（1）Suitable curing system, liquid body are configured to according to the conventional curing formula of thermosetting high-molecular organic material
System can directly stir；Pulverized solid system can directly be blended uniformly；Available times industrially commonly used of granulated solid system
What disintegrating apparatus is blended uniform after crushing.
（2）By the thermosetting high-molecular organic material system prepared, under conventional condition of cure, with any available
Equipment molding is in blocks, and not fully cured, thickness determines that upper and lower surface is equal by fixed bed catalyst or fluid catalyst size
Even cladding Raney alloy powder, continues to be molded to being fully cured, Raney alloy powder is by part press-in thermoset carrier, and thermosetting is carried
The surface of body sheet material is loaded by Raney alloy powder, that is, obtains loaded catalyst.
（3）By loaded catalyst obtained above, using any available high-molecular organic material process equipment, pass through
Cutting, cut, the particle that fixed bed or fluidized-bed reaction can be used, the particle diameter of particle are processed into punching press or the method such as broken
Size is on the basis of it can meet particle size needed for fixed bed catalyst or fluid catalyst, and the shape of particle can be
Any irregular shape, orbicule, hemispherical mass, cylinder, semi-cylindrical body, prism-shaped body, cube, cuboid, ring
Combination of shape body, half-annuli, hollow cylinder, tooth form or more shape etc., preferably spherical, annular, tooth form, cylinder or with
The combination of upper shape.
In method（ⅲ）Or method（ⅳ）, can be with described thermosetting high-molecular organic material curing system preparation process
Add optional one or more and be selected from following additive：It is curing accelerator, dyestuff, pigment, colouring agent, antioxidant, steady
Determine agent, plasticizer, lubricant, flow ability modifying agent or auxiliary agent, fire retardant, dripping inhibitor, anti-caking agent, adhesion promoter, conductive agent, multivalence
Metal ion, impact modifying agent, demolding aids, nucleator etc..Additive therefor consumption is conventional amount used, or according to actual feelings
The requirement of condition is adjusted.
The catalyst obtained according to the method described above can be easy to be activated, and activation condition is usually：At 25 DEG C~95 DEG C,
Use 0.5-30%（Weight）The aqueous slkali dissolution of concentration is selected from least one of aluminium, zinc and silicon, alkali lye preferably with NaOH or
KOH, about 5 minutes~72 hours base extraction time.
By controlling the activation degree of the addition of Raney alloy and/or control catalyst in catalyst preparation process, from
And the load capacity of Raney metal in catalyst can be easily controlled, it is 1~90% that can for example obtain Raney metal load capacity
（Weight）（Counted using overall catalyst weight as 100%）Activation loaded catalyst, preferably Ni content of metal be 10~80%（Weight
Amount）Activation loaded catalyst, more preferably Raney metal load capacity be 40~80%（Weight）.
Inorganic oxide carrier metal supported catalyst prepared by traditional use infusion process is, it is necessary to repeatedly impregnate, repeatedly
Roasting, process is complicated, and the load capacity of metal is difficult more than 40%（Weight）（Counted using overall catalyst weight as 100%）, and due to system
High-temperature roasting during standby causes considerable metallic particles to sinter so that the utilization rate of active metal is relatively low, thus catalysis
Agent activity is relatively low.Although the catalyst of high metal content can be obtained using blending method or coprecipitation, due to a large amount of metals
Wrapped up by inactive ingredients, the utilization ratio of metal is very low, thus cause the activity of catalyst very low.Catalyst of the present invention is not only
More active metals can be loaded, and do not have high-temperature process in preparation process, so the utilization rate of active metal is very high, thus
Catalyst activity is high.
The thunder Buddhist nun Ni catalyst of described organic polymer load is preformed catalyst, and intensity is good, can be used for fixed bed
Bed catalytic reaction.
Method of hydrotreating of the present invention, available for reaction of the decenal Hydrogenation for decyl alcohol, wherein decenal can be
2- propyl group heptenals, 4- methyl-2-propyl hexenoic aldehydes, 5- methyl-2-propyl hexenoic aldehydes, 2- isopropyl-4-methyl hexenoic aldehydes etc..
The essential distinction of the present invention and prior art are that the oxide carried Ni that Traditional liquid phase aldehyde hydrogenation is used is urged
Agent, it is difficult to while meeting high activity and high selectivity.The present invention uses two step hydrogenation methods, and second step is hydrogenated with using organic high
Thunder Buddhist nun's Ni catalyst of molecule load, high activity and high selectivity can be met simultaneously, and hydrogenation depth is big, and olefine aldehydr is remained very in product
Few, hydrogenated products quality is good, and product yield is high.
Embodiment
Following examples are citing descriptions more detailed to the present invention, but the invention is not limited in these embodiments.
The catalyst preparation of embodiment 1（Thunder Buddhist nun's Ni catalyst A of macromolecule loading）
（1）By polypropylene powder（Maoming Petrochemical, F280M）Φ 3mm × 3~5mm is extruded and chopped into double screw extruder
Particle；
（2）Weigh 100g PP GRANULESs to be placed among nickel alumin(i)um alloy powder, Ni contents are 48% in nickel alumin(i)um alloy（Weight
Amount）, aluminium weight content 52%（Weight）, 10min is molded under conditions of 200 DEG C of temperature, pressure 7MPa with compression molding instrument, is taken
Go out cooling, sieving sifts out spherical particle, particle surface is covered by Nickel Aluminium Alloy Powder completely, that is, is obtained loaded catalyst, weighed
For 380g；
（3）20%NaOH aqueous solution 400g are configured with deionized water, step is added（2）Gained catalyst 40g, keeping temperature
Filter out solution after 85 DEG C, 4 hours, that is, the catalyst activated, nickel content of metal is about 56% in final catalyst（Weight
Amount）, after washing to close neutrality, deposit in standby in deionized water.
The catalyst preparation of embodiment 2（Thunder Buddhist nun's Ni catalyst B of macromolecule loading）
（1）Weigh 100g nylon -66 particles（Ba Ling petrochemical industry, BL2340-H）It is placed among nickel alumin(i)um alloy powder, nickel aluminium is closed
Ni contents are 48% in gold（Weight）, aluminium content 52%（Weight）, with compression molding instrument in 250 DEG C of temperature, pressure 7MPa condition
Lower molding 10min, takes out cooling, and sieving sifts out spherical particle, particle surface is covered by Nickel Aluminium Alloy Powder, that is, born completely
Supported catalyst, is weighed as 350g；
（2）20%NaOH aqueous solution 400g are configured with deionized water, step is added（1）Gained catalyst 40g, keeping temperature
Filter out solution after 85 DEG C, 4 hours, that is, the loaded catalyst activated, nickel content of metal is about in final catalyst
45%（Weight）, after washing to close neutrality, deposit in standby in deionized water.
The catalyst preparation of embodiment 3（The Ni catalyst of alumina load）
The nickel-metal catalyst of alumina load is prepared by pressed disc method.First by 1kg basic nickel carbonates NiCO3·2Ni
(OH)2·4H2O is calcined with after a certain amount of boehmite kneading, drying, granulation, and compression molding is Φ 3mm × 3mm cylinders
Contain 56% in shape catalyst granules, reduction rear catalyst（Weight）Nickel metal, for fixed bed hydrogenation reaction.
The aldehyde liquid-phase hydrogenatin reactivity worth of embodiment 4 is tested（The two steps hydrogenation of the present invention）
First step hydrogenation uses the catalyst of embodiment 3, and second step hydrogenation uses the catalyst of embodiment 2.First step hydrogenation behaviour
Make：Use fixed bed decenal（2- propyl group heptenals）Catalyst reaction performance is evaluated in liquid-phase hydrogenatin, takes catalyst 20ml to load
Fixed bed reactors, hydrogen flowing quantity is 200ml/min, 140 DEG C of reaction temperature, pressure 4.0MPa, hutanal liquid air speed 1.0h-1。
Second step hydroprocessing：The catalyst 20ml of Example 2 loads fixed bed reactors, and hydrogen flowing quantity is 100ml/min, reaction temperature
110 DEG C of degree, pressure 4.0MPa, liquid air speed 1.0h-1, reactant uses first step hydrogenation products, wherein main unsaturates is
2- propyl group heptenals, reaction product is quantitative using gas-chromatography, and chromatographic detector is FID.Hydrogenation reaction the results are shown in Table 1.Contrast
Example aldehyde liquid-phase hydrogenatin reactivity worth test（One step is hydrogenated with）
The catalyst of embodiment 3 is only used, step hydrogenation uses fixed bed decenal（2- propyl group heptenals）Liquid-phase hydrogenatin is commented
Valency catalyst reaction performance, takes catalyst 20ml to load fixed bed reactors, hydrogen flowing quantity is 200ml/min, reaction temperature 140
DEG C, pressure 4.0MPa, hutanal liquid air speed 1.0h-1, reaction product is quantitative using gas-chromatography, and chromatographic detector is FID.Hydrogenation
Reaction result is shown in Table 1.
The aldehyde liquid-phase hydrogenatin reactivity worth of comparative example 2 is tested（Two steps are hydrogenated with）
Use the catalyst of embodiment 3, two steps hydrogenation.First step hydroprocessing：Use fixed bed decenal（2- propyl group heptene
Aldehyde）Catalyst reaction performance is evaluated in liquid-phase hydrogenatin, and the catalyst 20ml of Example 3 loads fixed bed reactors, and hydrogen flowing quantity is
200ml/min, 140 DEG C of reaction temperature, pressure 4.0MPa, hutanal liquid air speed 1.0h-1.Second step hydroprocessing：Example 3
Catalyst 20ml loads fixed bed reactors, and hydrogen flowing quantity is 100ml/min, 110 DEG C of reaction temperature, pressure 4.0MPa, liquid
Air speed 1.0h-1, reactant uses first step hydrogenation products, wherein main unsaturates is 2- propyl group heptenals, reaction product makes
Quantitative with gas-chromatography, chromatographic detector is FID.Hydrogenation reaction the results are shown in Table 1.
The decenal liquid-phase hydrogenatin reaction result of table 1 is contrasted
From evaluation result, the hydrogenated products residual olefine aldehydr that the two steps hydrogenation that the present invention is used is obtained is few, product quality
Good, product yield is high.
Claims (8)
1. a kind of method that decenal liquid-phase hydrogenatin prepares decyl alcohol, first step hydrogenation is existed using at least one liquid phase hydrogenation reactor
Carried out on first catalyst, the first described catalyst is oxide carried Ni systems or Cu series catalysts, it is characterised in that the
Two steps hydrogenation is carried out using at least one liquid phase hydrogenation reactor on the second catalyst, and the second described catalyst is organic high
Thunder Buddhist nun's Ni catalyst of molecular vehicle load；
The second described catalyst includes organic polymeric carrier material, is supported on the Raney alloy of organic polymer carrier surface
Particle, wherein described Raney alloy particle fraction is embedded in organic polymeric carrier material, the load capacity of active metal is 40
~80wt%；
The preparation method of the second described catalyst is under high-molecular organic material carrier processing and forming temperature conditionss or not solid
Change under conditions of sizing, be molded the high-molecular organic material coated by Raney alloy particle.
2. the method that a kind of decenal liquid-phase hydrogenatin according to claim 1 prepares decyl alcohol, it is characterised in that described thunder
Damping alloy is nickel alumin(i)um alloy, nickel silicon alloy.
3. the method that a kind of decenal liquid-phase hydrogenatin according to claim 1 prepares decyl alcohol, it is characterised in that described thunder
Damping alloy also includes accelerator, and accelerator is selected from least one of Mo, Cr, Ti, Fe, Pt, Pd, Rh, Ru, and the amount of accelerator is
0.01~5wt% of Raney alloy total amount.
4. the method that a kind of decenal liquid-phase hydrogenatin according to claim 1 prepares decyl alcohol, it is characterised in that described has
Machine polymeric carrier material is plastics or its modified product.
5. the method that a kind of decenal liquid-phase hydrogenatin according to claim 4 prepares decyl alcohol, it is characterised in that described has
Machine polymeric carrier material is at least one in polypropylene, nylon-6, nylon -66, polystyrene, phenolic resin and epoxy resin
Kind.
6. the method that a kind of decenal liquid-phase hydrogenatin according to claim 1 prepares decyl alcohol, it is characterised in that the first step adds
Hydrogen reaction temperature be 50 DEG C -200 DEG C, reaction pressure is 0.5-8.0MPa, using the reaction velocity of the liquid volume metering of aldehyde as
0.05-5.0h-1, hydrogen is 200~10000 with aldehyde volume ratio:1；Second step hydrogenation reaction temperature is 50 DEG C -200 DEG C, reaction pressure
Power is 0.5-8.0MPa, and the reaction velocity using the liquid volume metering of aldehyde is 0.05-5.0h-1, hydrogen and aldehyde volume ratio be 200~
10000:1。
7. the method that a kind of decenal liquid-phase hydrogenatin according to claim 6 prepares decyl alcohol, it is characterised in that the first step adds
Hydrogen reaction temperature be 90 DEG C -150 DEG C, reaction pressure is 3.0-5.0MPa, using the reaction aldehyde air speed of the liquid volume metering of aldehyde as
0.1-2.0h-1, hydrogen is 600~2000 with aldehyde volume ratio:1, second step hydrogenation reaction temperature is 90 DEG C -150 DEG C, reaction pressure
For 3.0-5.0MPa, the reaction velocity using the liquid volume metering of aldehyde is 0.1-2.0h-1, hydrogen and aldehyde volume ratio be 600~
2000:1。
8. the method that a kind of decenal liquid-phase hydrogenatin according to claim 1 prepares decyl alcohol, it is characterised in that the described last of the ten Heavenly stems
Olefine aldehydr be 2- propyl group heptenal, 4- methyl-2-propyls hexenoic aldehyde, 5- methyl-2-propyls hexenoic aldehyde, 2- isopropyl-4-methyls oneself
Olefine aldehydr.
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| GB649554A (en) * | 1948-10-13 | 1951-01-31 | Distillers Co Yeast Ltd | Improved process for the hydrogenation of unsaturated aldehydes |
| CN1037283A (en) * | 1988-04-14 | 1989-11-22 | 格雷斯公司 | The catalyst of moulding and preparation method |
| CN1333201A (en) * | 2000-07-14 | 2002-01-30 | 奥克森诺奥勒芬化学股份有限公司 | Multi-stage preparation process of carbonyl synthesizing aldehyde and/or alcohol |
| CN101396665A (en) * | 2007-09-26 | 2009-04-01 | 汉能科技有限公司 | Fixed bed Raney catalyst, preparation method and modification method thereof |
| CN102666455A (en) * | 2009-10-15 | 2012-09-12 | 赢创奥克森诺有限责任公司 | Method for producing decanols by means of hydrogenating decenals |
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