CN108191610A - A kind of preparation method of branched paraffin in the range of renewable lauryl alcohol and aviation kerosine - Google Patents
A kind of preparation method of branched paraffin in the range of renewable lauryl alcohol and aviation kerosine Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of the branched paraffin in the range of biomass-based lauryl alcohol and aviation kerosine.The present invention is divided into two parts：1) in the first catalyst bed of fixed bed flow reactor, the mixture of two or more in isopropylidene acetone, diacetone alcohol, methyl isobutyl carbinol or more compound is under the catalysis of acid catalyst, base catalyst, metal-doped solid acid catalyst or metal-doped solid base catalyst, by condensation reaction, the oxygen-containing organic compound that carbon chain lengths are 12 is obtained；2) on the second catalyst bed of fixed bed flow reactor, the condensation product and unreacted hydrogen of the generation of the first catalyst bed carry out hydrogenation reaction under the promotion of relatively low reaction temperature and metallic catalyst, obtain lauryl alcohol.
Description
Technical field
The present invention relates to a kind of preparation methods of the branched paraffin in the range of renewable lauryl alcohol and aviation kerosine, specific to wrap
Include two steps：1) in the first catalyst bed of fixed bed flow reactor, lignocellulose biomass platform chemicals
Two or more mixture and hydrogen in isopropylidene acetone, diacetone alcohol, methyl isobutyl carbinol or these compounds
Gas under the promotion of acid catalyst, base catalyst, metal-doped solid acid catalyst or metal-doped solid base catalyst,
The oxygen-containing organic compound that carbon chain lengths are 12 is obtained by condensation reaction；2) in the second catalysis of fixed bed flow reactor
On agent bed, the oxygen-containing organic compound that the first catalyst bed generation carbon chain lengths are 12 is difunctional in carried metal A/X types
By adding the branch that hydrogen or hydrogenation deoxidation can obtain renewable lauryl alcohol respectively or carbon chain lengths are 12 under the promotion of catalyst
Alkane.The lauryl alcohol obtained by the present invention may be used as synthetic surfactant dodecyl sodium sulfate or detergent alkylate sulphur
The intermediate of sour sodium, and the branched paraffin that the carbon chain lengths that obtain of the present invention are 12 can be used with traditional aviation kerosine be used in mixed way with
Alleviate degree of dependence of the China to imported crude oil.Compared with the work having been reported, this work first passage flow reactor
Dual bed catalyst is under relatively mild conditions in isopropylidene acetone, diacetone alcohol, methyl isobutyl carbinol or these compounds
Two or more mixture and hydrogen directly synthesize the branched paraffin in the range of lauryl alcohol or aviation kerosine, tool for raw material
There are the advantages such as simple for process, efficient, energy saving.
Background technology
In recent years, energy and environmental problem receives significant attention, using the neutral biomass of renewable, carbon dioxide as raw material
The work of synthetic fuel and energy chemistry product is paid much attention to by countries in the world.Gasoline, diesel oil, aviation kerosine are the current worlds
The huge transport fuel of upper demand.At present, gasoline, diesel oil, aviation kerosine crack, reformation etc. mainly with crude oil through rectifying
Technique is prepared, and has non-renewable.Also, fossil energy obtains gasoline, diesel oil, aviation fuel and in use can
Additional carbon dioxide is discharged to air, causes greenhouse effects.Therefore, it from sustainable development, environmental protection etc. consideration, needs
Greatly develop using the neutral biomass of renewable, carbon dioxide as raw material by catalyzed conversion prepare gasoline, aviation kerosine and
The new technology of diesel oil.On the other hand, fatty alcohol is a kind of important fine chemicals, be widely used in surfactant, fragrance,
In the preparation of the products such as cosmetics.How much low carbon fat alcohol, middle carbon fatty alcohol and high-carbon fatty alcohol are divided into according to carbon atom number.Its
Middle carbon fatty alcohol refers to C12-C14Aliphatic alcohols, be detergent surfactant primary raw material.Lignocellulosic is agriculture
The main component of woods waste has advantage that is cheap, deriving from a wealth of sources compared with the biomass of other forms.Therefore, closely
Year over lignocellulosic prepare gasoline, aviation kerosine or fine chemicals flourish and have become international bio matter catalysis refining
One important research direction of system.
At present, biomass lauryl alcohol is mainly by adding hydrogen to obtain palm oil.It is the limited source of raw material, expensive, no
It is suitble to large-scale production, needs to develop the renewable lauryl alcohol synthetic technology using cheap lignocellulosic as raw material.It is and international
Upper existing lignocellulosic aviation fuel synthetic technology is mainly set out with platform chemicals, and carbon is obtained by C-C coupling reaction
Chain length is the aviation kerosine precursor of 8-16, then by the way that these aviation kerosine precursor hydrogenation deoxidations are reacted with synthesis aviation coal
The alkane of oily range.Complex process, equipment investment are larger.It needs to heat different reactants in two-step reaction and right
Product repeats to cool down, and energy consumption is larger.The separation of catalyst and the rectifying of product, cost are higher.Therefore, it is intended that find life
The alkane of substance platform chemicals one-step synthesis method aviation kerosine range and the route of aliphatic alcohols.
In this patent, we are made using the mixed feeding of propylidene acetone, diacetone alcohol or propylidene acetone and diacetone alcohol
For raw material, propylidene acetone and diacetone alcohol can be obtained by biomass lignocellulosic by acetone-butanol-ethanol (ABE) fermentation
Acetone set out, obtained through self-condensation.The process technology maturation.Compared to hexone, propylidene acetone and
Diacetone alcohol is the product of acetone self-condensation, and synthesis technology is simpler, less expensive in cost.Methyl isobutyl carbinol be with
Acetone is the by-product of Material synthesis hexone, while is also a pair during the present invention synthesizes lauryl alcohol
Product, price is also relatively inexpensive at present.
In the first catalyst bed of fixed bed flow reactor, biomass platform chemicals isopropylidene acetone, double third
Two or more mixture and hydrogen in keto-alcohol, methyl isobutyl carbinol or these compounds is in acid catalyst, alkali
It is anti-by self-condensation under the catalysis of catalyst, metal-doped solid acid catalyst or metal-doped solid base catalyst
Should, obtain the oxygen-containing organic compound that carbon number is 12；2) on the second catalyst bed of fixed bed flow reactor, first
Catalyst bed generation condensation product can obtain ten under the promotion of carried metal A/X type bifunctional catalysts by hydrogenation reaction
Glycol reacts the branched paraffin obtained in the range of aviation kerosine by hydrogenation deoxidation.Whole process is using isopropylidene acetone, double
Two or more mixture and hydrogen in pyruvic alcohol, methyl isobutyl carbinol or these compounds is direct as raw material
The separation that target product avoids catalyst and product is obtained, by the temperature for adjusting the second bed catalyst, so that it may adjust production
Object is distributed, and is realized chemical industrial integrated, is conducive to the industrialization continuous production of following lauryl alcohol, aviation kerosine.
Invention content
The purpose of the present invention is to provide one kind from lignocellulosic derivative compound, prepare renewable lauryl alcohol or
Branched paraffin in the range of aviation kerosine it is novel, simply, efficient synthetic route.
The present invention is achieved by the following technical solutions：
Lauryl alcohol or aviation kerosine model are directly synthesized under relatively mild conditions using flow reactor dual bed catalyst
Enclose interior branched paraffin.
1) it is biomass platform chemicals isopropylidene acetone, double in the first catalyst bed of fixed bed flow reactor
Two or more mixture and hydrogen in pyruvic alcohol, methyl isobutyl carbinol or these compounds acid catalyst,
Under the catalysis of base catalyst, metal-doped solid acid catalyst or metal-doped solid base catalyst, by condensation reaction,
Obtain the oxygen-containing organic compound that carbon number is 12；In this patent, we are different using isopropylidene acetone, diacetone alcohol or methyl
Butyl carbinol or their mixture can pass through third as raw material, propylidene acetone and diacetone alcohol by biomass lignocellulosic
The acetone that ketone-butanol-ethyl alcohol (ABE) fermentation obtains sets out, and is obtained through itself aldol condensation.Methyl isobutyl carbinol is with acetone
For the by-product of Material synthesis methyl iso-butyl ketone (MIBK) reaction process, while it is also one during present invention synthesis lauryl alcohol
By-product.
2) on the second catalyst bed of fixed bed flow reactor, the carbon number of the first catalyst bed generation is 12
Oxygen-containing organic compound and unreacted hydrogen under the promotion of carried metal A/X type bifunctional catalysts by the way that hydrogen is added to obtain
Lauryl alcohol reacts the branched paraffin obtained in the range of the aviation kerosine that carbon chain lengths are 12 by hydrogenation deoxidation.
Acid catalyst described in first catalyst bed is one or two or more kinds of mixtures in following solid acids：Acid
Property resin is (such as：Amberlyst-15, Amberlyst-16, Amberlyst-36, Amberlyst-45, Amberlyst-70),
Acidic molecular sieve is (such as：H-ZSM-5, H- β, H-MOR, H-Y etc.), the metal oxide of phosphorylation is (such as：Phosphorylation zirconium oxide, phosphorus
It is acidified niobium oxide etc.), acidic metal oxide is (such as：Niobium oxide, tantalum oxide, montmorillonite K-10 or KSF etc.)；
Base catalyst described in first catalyst bed is one or two or more kinds of mixtures in following solid bases：Gu
Body alkali includes alkaline metal oxide (such as：MgO、CaO、SrO、La2O3、CeO2Deng) alkalinous metal composite oxides are (such as：Magnalium
Hydrotalcite, lithium aluminum hydrotalcite, loading 10-60wt% KF/Al2O3, Mg/Zr atoms number is than the MgO-ZrO for 1-202
Deng), alkaline molecular sieve is (such as：Na-Y, Na-ZSM-5, Na-MOR, Na-MCM-41 etc.), deacidite is (such as：Dowex
1 × 4, Dowex 1 × 2, Amberlite IRA-900, Amberlite IRA-400 etc.)；
Metal-doped solid acid described in first catalyst bed is cobalt, the doping of nickel, copper, silver, palladium, platinum, ruthenium, iridium, rhodium
Solid acid one or more kinds of mixtures.
Metal-doped solid base described in first catalyst bed is cobalt, the doping of nickel, copper, silver, palladium, platinum, ruthenium, iridium, rhodium
Solid base one or more kinds of mixtures.
Using the difunctional A/X types catalyst of load type metal as the second catalyst bed described in second catalyst bed
Directly to isopropylidene acetone, diacetone alcohol, methyl isobutyl carbinol or isopropylidene acetone, diacetone alcohol, methyl isobutyl carbinol
Or more in compound the condensation reaction products of two or more mixture carry out plus hydrogen or hydrogenation deoxidation；Carrier X is
One or two or more kinds of mixtures in following substances：Activated carbon, silica, sial complex carrier SiO2-Al2O3(silica alumina ratio
Between 0.01-100), molecular sieve (such as：H-Y, HZSM-5, H β, HMOR etc.), the metal oxide of phosphorylation is (such as：Phosphorylation
Zirconium oxide, phosphorylation niobium oxide, phosphorylation tantalum oxide etc.), acidic metal oxide is (such as：Niobium oxide, titanium oxide, tantalum oxide
Deng)；Active component A is one or more of Fe, Co, Ni, Cu, Pt, Pd, Ru, Ir, Rh；Active component A is in catalyst
In mass fraction 1-50% (preferably 30-50%).；
The condition of fixed bed reactors is：When preparing lauryl alcohol, the first bed catalyst temperature is (excellent between 100-500 DEG C
Select 200-400 DEG C), the second bed catalyst temperature (preferably 60-200 DEG C) between 50-250 DEG C, reaction Hydrogen Vapor Pressure is in 0.1-
Between 10.0MPa (preferably 0.1-1.0MPa), the bed catalyst mass space velocity of raw material/first is in 0.1-10.0h-1(preferably 0.1-
5h-1), the bed catalyst mass space velocity of raw material/second is in 0.1-10.0h-1(preferably 0.1-5h-1)H2With mole of substrate raw material
Than for 1-800 (preferably 1-200).
When preparing branched paraffin in the range of aviation kerosine, fixed bed reactors temperature (preferably 200- between 100-500 DEG C
400 DEG C), reaction Hydrogen Vapor Pressure (preferably 0.1-1.0MPa) between 0.1-10.0MPa, the bed catalyst quality of raw material/first
Air speed is in 0.1-10.0h-1(preferably 0.1-5h-1), the bed catalyst mass space velocity of raw material/second is in 0.1-10.0h-1(preferably
0.1-5h-1)H2Molar ratio with substrate raw material is 1-800 (preferably 1-200).
The present invention is divided into two parts：1) in the first catalyst bed of fixed bed flow reactor, isopropylidene acetone,
The mixture of two or more in diacetone alcohol, methyl isobutyl carbinol or more compound is in acid catalyst, base catalysis
Under the catalysis of agent, metal-doped solid acid catalyst or metal-doped solid base catalyst, by condensation reaction, carbon is obtained
Chain length is 12 oxygen-containing organic compound；2) on the second catalyst bed of fixed bed flow reactor, the first catalysis
The condensation product and unreacted hydrogen of agent bed generation are added under the promotion of relatively low reaction temperature and metallic catalyst
Hydrogen reacts, and obtains lauryl alcohol.In addition, on the second catalyst bed of fixed bed flow reactor, the first catalyst bed
The condensation product of generation and unreacted hydrogen can also pass through the rush of metallic catalyst at the temperature identical with condensation reaction
The branched paraffin that carbon chain lengths are 12 is obtained into lower progress hydrogenation deoxidation reaction.The lauryl alcohol obtained by the present invention can pass through
Sulfonated synthetic surfactant dodecyl sodium sulfate can also obtain the main component 12 that synthetic washing takes by dehydration
One of primary raw material of sodium alkyl sulfonate-laurylene.The branched paraffin for being 12 by the carbon chain lengths that the present invention obtains, can make
Potential substitute for aviation kerosine or diesel oil；
It, can be directly in isopropylidene acetone, diacetone alcohol, methyl isobutyl carbinol or these compounds by above step
Two or more mixture and hydrogen selectively obtain branch in the range of lauryl alcohol or aviation kerosine for raw material
Alkane, more than 70% yield, high selectivity.It is one and prepares fatty alcohol as raw material using platform chemicals derived from lignocellulosic
Or efficient, green, the easy new synthesis route of the branched paraffin in the range of aviation kerosine.
The branched paraffin in the range of the aviation kerosine of carbochain a length of 12 is obtained by the present invention can become existing aviation kerosine
Or the potential substitute of diesel oil；Synthesising biological matter based surfactants dodecyl can be used for by the lauryl alcohol that the present invention obtains
The raw material of sodium sulfonate, neopelex etc..
Description of the drawings
The GC-MS spectrograms of Fig. 1 isopropylidene acetone autohemagglutination products；
Fig. 2 isopropylidene acetone autohemagglutination products add the GC-MS spectrograms of hydrogen；
The GC spectrograms of Fig. 3 isopropylidene acetone autohemagglutination products；
The GC spectrograms of Fig. 4 isopropylidene acetone autohemagglutination product hydrogenation deoxidations；
Fig. 5 isopropylidene acetone autohemagglutination products add the GC spectrograms of hydrogen.
Specific embodiment
The present invention will be illustrated, but protection scope of the present invention is not limited to these with specific embodiment below
Example.
Embodiment 1-14
1. the preparation of catalyst：
1) preparation of solid acid catalyst：Nafion and Amberlyst resins, Y type molecular sieve, montmorillonite K-10 and KSF
For the commercial catalysts product directly bought.
Phosphorylation zirconium oxide (ZrP) catalyst be by the zirconium oxychloride of 1mol/L and ammonium dihydrogen phosphate aqueous solution by volume
2:1 mixing, obtained precipitation dry 10h after washing filtering repeatedly at 120 DEG C, then roast 4h at 400 DEG C.
2) preparation of solid base catalyst：Alkaline-earth oxide (MgO, CaO, SrO) and rare earth oxide (La2O3、CeO2) point
Not by corresponding nitrate in N28h is calcined under atmosphere to obtain.
Magnalium hydrotalcite is by quality 0.093mol Mg (NO3)2·6H2O and 0.0465mol Al (NO3)3·9H2O is dissolved in
In 100ml water, solution is under 70 DEG C of water bath conditions by 0.219mol NaOH and 0.0565mol Na2CO3100ml it is water-soluble
Drop is added thereto, and is continued to stir age overnight after completion of dropwise addition, is dried overnight for 80 DEG C after filtration washing, and 450 DEG C of calcining 8h are obtained
To magnalium mixed oxide.Lithium aluminum hydrotalcite is by 125mL Al (NO in room temperature3)3·9H2The aqueous solution of O (0.4mol/L) by
The 300mL LiOHH being added dropwise in being stirred continuously2O (1.5mol/L) and Na2CO3In (0.08mol/L) mixed solution.It is added dropwise
Finish at 75 DEG C aging for 24 hours.It is dried overnight for 80 DEG C after filtration washing, 500 DEG C of calcining 8h obtain lithium aluminium-mixed oxide.
KF/Al2O3By equi-volume impregnating by γ-Al2O312h in KF solution is immersed in, theoretical matter is obtained after 80 DEG C of dryings
Measure the KF/ γ-Al of loading 23%2O3。
MgO-ZrO225wt%NaOH solution is added drop-wise to dissolved with 50.9g Mg (NO3)2·6H2O and 4.04g ZrO (NO3)2
1L solution in pH=10, aged at room temperature 72h, filtration washing, 80 DEG C are dried overnight, 600 DEG C of calcining 8h.All solids alkali is urged
Agent is using being preceding intended in N22h is pre-processed in atmosphere.
3) metal-doped solid acid：
By taking metal-doped HY molecular sieves as an example.Respectively prepare mass fraction be 5wt% metal salt solution (cobalt nitrate,
One or more of nickel nitrate, copper nitrate, palladium nitrate, platinum chloride, ruthenic chloride, iridium chloride etc.), it is inhaled according to carrier saturation
Water dilutes, and HY molecular sieve incipient impregnations is stood overnight, 80 DEG C of dryings, roasts 2h at 500 DEG C, the catalyst after roasting
Hydrogen in-situ reductase 12 h is used at 500 DEG C in fixed bed.
4) metal-doped solid base：
By taking metal-doped magnalium hydrotalcite catalyst as an example.It is 0.093molMg (NO by mass concentration3)2·6H2O and
0.0465mol Al(NO3)3·9H2O is dissolved in 100ml water, then by the salting liquid (nitre containing 0.001mol-0.01mol metals
One or more of sour cobalt, nickel nitrate, copper nitrate, palladium nitrate, platinum chloride, ruthenic chloride, iridium chloride etc.) instill the mixing
In solution, solution is under 70 DEG C of water bath conditions by 0.219mol NaOH and 0.0565mol Na2CO3100ml aqueous solutions be added dropwise
Enter wherein, continue to stir age overnight after completion of dropwise addition, be dried overnight for 80 DEG C after filtration washing, 450 DEG C of calcining 8h are mixed
Oxide.
5) preparation of hydrogenation deoxidation catalyst：
Equi-volume impregnating：It is molten that ferric nitrate, cobalt nitrate, nickel nitrate, copper nitrate that mass fraction is 5wt% are prepared respectively
Liquid is diluted according to carrier saturated water adsorptive value, its one or more is added in silica incipient impregnation, is stood overnight, 80 DEG C
It is dry, 2h is roasted at 500 DEG C, the catalyst after roasting uses hydrogen in-situ reductase 12 h in fixed bed at 500 DEG C.(1 is shown in Table,
Embodiment 1-4).Platinum chloride, palladium nitrate, the chlorination ruthenium solution that mass fraction is 5wt% are prepared respectively, are absorbed water according to carrier saturation
Its one or more is added in H- beta-molecular sieve incipient impregnations, stands overnight, 80 DEG C of dryings, 2h is roasted at 500 DEG C by amount dilution,
Catalyst after roasting uses hydrogen in-situ reductase 12 h in fixed bed at 500 DEG C.(being shown in Table 1, embodiment 5-7).
The nickel nitrate solution of mass ratio 5wt% is prepared respectively, is diluted, added accordingly according to the saturated water adsorptive value of carrier
Enter one kind in H-ZSM-5, H-MOR, sial complex carrier, H- beta-molecular sieves, aluminium oxide, then stand 2h, done at 120 DEG C
Dry overnight, in 500 DEG C of air roasting 2h, the catalyst after roasting uses hydrogen in-situ reductase 12 h in fixed bed at 500 DEG C.
(being shown in Table 1, embodiment 8-12).
Infusion process is complexed：Prepare respectively mass fraction for 5wt% nickel nitrates ethylene glycol and water mixed solution (ethylene glycol with
Salt ion equimolar amounts), it is separately added into silica, H-ZSM-5, H-MOR, sial complex carrier, H- beta-molecular sieves, oxygen
Change a kind of incipient impregnation in aluminium, stand overnight, 80 DEG C of dryings roast 2h at 500 DEG C, and the catalyst after roasting is in fixation
Hydrogen in-situ reductase 12 h is used in bed at 500 DEG C.(being shown in Table 1, embodiment 13)
Deposition-precipitation method：The nickel nitrate solution of preparation 0.0175M, which is divided into equal volume in two parts A and B, A, respectively adds in two
Silica, H-ZSM-5, H-MOR, sial complex carrier, H- beta-molecular sieves, one kind in aluminium oxide and appropriate concentrated nitric acid, in B plus
Enter 0.0525M urea, B is slowly added dropwise into A in 80 DEG C of water-baths, 10h is stirred after being warming up to 90 DEG C, filtration washing, 80 DEG C dried
At night, in 500 DEG C of air roasting 2h, the catalyst after roasting uses hydrogen in-situ reductase 12 h in fixed bed at 500 DEG C.It (is shown in Table
1, embodiment 14-16,16A, 16B)
1 carried metal A/X type bifunctional catalysts of table
2 self-condensations react：In fixed bed reactors, 1.0g catalyst is fitted into reaction tube, is kept in reactor
Hydrogen Vapor Pressure is 0.6MPa, hydrogen flow rate 150mL/min, and propylidene acetone is pumped into efficient liquid-phase chromatographic pump with 0.05mL/min
In reactor.Reaction result is shown in Table 2 and table 3.
2 propylidene acetone self-condensation reaction result of table
As can be seen from Table 2, solid acid, the basic catalyst mixed without metal, to propylidene acetone self-polymeric reaction activity
It is undesirable.When in doped precious metal on acid or base catalyst (embodiment 17-35), ketone, the alcohol of 12 carbon can be generated.Wherein when
Activity is preferable when adulterating the magnalium hydrotalcite of Pd.
3 self-condensation of table reacts target product structural formula
Embodiment 36-41
For the magnalium hydrotalcite (Pd-MgAl-HT) for choosing palladium doping, the optimization for carrying out reaction condition is explored.
1) influence of the palladium/magnesium molar ratio to propylidene acetone self-condensation reaction yield
Influence of the 4 catalyst quality score of table to products collection efficiency
As can be seen from Table 4, when palladium/magnesium molar ratio is 0.02, product total recovery highest.
Embodiment 42-46
2) influence of the differential responses temperature to isopropylidene acetone self-condensation reaction yield
Influence of the 5. differential responses temperature of table to products collection efficiency
As can be seen from Table 5, when reaction temperature is 250-280 DEG C, product B yields are higher, and yield summation is higher.
Embodiment 47-50
3) influence of the different hydrogen pressure to isopropylidene acetone self-condensation reaction yield
Influence of the 6. different hydrogen pressure of table to products collection efficiency
As can be seen from Table 6, when Hydrogen Vapor Pressure is 0.6MPa, target product B, C total recovery is higher.
Embodiment 51-57
4) influence of the different feeds component to yield
Influence of the 7. different feeds component of table to products collection efficiency
As can be seen from Table 6, isopropylidene acetone and the variation of diacetone alcohol molar ratio influence not product B, C total recovery
Greatly, this is conducive in industry directly feed without separation directly by the isopropylidene acetone of condensation of acetone, diacetone alcohol mixture.
It in addition, can also higher yields acquisition B and C using the by-product methyl isobutyl carbinol (product D) in this reaction.In practical life
It can be by further improving B, C total recovery to the recycling of product D in production.
3. hydrogenation deoxidation reacts：
Embodiment 58-75
1) influence that different catalysts react hydrogenation deoxidation
In fixed bed reactors, by 1.0g isopropylidene acetone self-condensation catalyst (by taking Pd-MgAl-HT as an example) as
First catalyst bed, 1.5g hydrogenation deoxidation catalysts are fitted into as the second catalyst bed in reaction tube, are kept in reactor
Pressure is 0.6MPa, hydrogen flow rate 150mL/min, 280 DEG C of reaction temperature, isopropylidene acetone efficient liquid-phase chromatographic pump with
0.05mL/min is pumped into reactor.Reaction result is shown in Table 9.
8 hydrogenation deoxidation of table reacts target product structural formula
As can be seen from Table 9, under the reaction conditions, the hydrogenation deoxidation of product can be achieved in selected catalyst.By adding
The principal product F that hydrogen deoxidation obtains is aviation kerosine range branched paraffin.By-product E may be used as renewable gasoline.
Influence of the 9 difference A/X types bifunctional catalyst of table to hydrogenation deoxidation reactivity
Embodiment 76-80
2) influence that different temperatures reacts hydrogenation deoxidation
In fixed bed reactors, by 1.0g isopropylidene acetone self-condensation catalyst (by taking Pd-MgAl-HT as an example) as
First catalyst bed, 1.5g hydrogenation deoxidation catalysts 5%Cu/SiO2It is fitted into reaction tube, protects as the second catalyst bed
It is 0.6MPa to hold pressure in reactor, and hydrogen flow rate 150mL/min, isopropylidene acetone efficient liquid-phase chromatographic pump is with 0.05mL/
Min is pumped into reactor.Reaction result is shown in Table 10.
Influence of 10 different temperatures of table to hydrogenation deoxidation reactivity
As can be seen from Table 10, when temperature is less than 250 DEG C, oxygenatedchemicals is unable to complete hydrogenation deoxidation, when temperature is big
When equal to 250 DEG C, oxygenatedchemicals can complete hydrogenation deoxidation.When wherein with 250-280 DEG C, yield highest.
4. hydrogenation reaction：
Embodiment 81-92
1) influence of the different catalysts to hydrogenation reaction
In fixed bed reactors, by 1.0g isopropylidene acetone self-condensation catalyst (by taking Pd-MgAl-HT as an example) as
First catalyst bed (250 DEG C of bed temperature), 1.5g hydrogenation catalysts are as the second catalyst bed (100 DEG C of bed temperature)
It is fitted into reaction tube, it is 0.6MPa, hydrogen flow rate 150mL/min to keep pressure in reactor, by the efficient liquid of isopropylidene acetone
Phase chromatogram pump is pumped into 0.05mL/min in reactor.Reaction result is shown in Table 11.
Influence of the 11 difference A/X types bifunctional catalyst of table to hydrogenation reaction activity
As can be seen from Table 11, activated carbon but palladium, ruthenium, iridium catalyst reactivity it is preferable, the first bed can be given birth to
Into ketone complete hydrogenation be alcohol.Wherein product B can be used as synthetic surfactant dodecyl sodium sulfate or dodecyl
The raw material of benzene sulfonic acid sodium salt, product D may be used as mineral flotation agent, while also recycling continues to improve the yield of product B.
Embodiment 93-97
2) influence of the different temperatures to hydrogenation reaction
In fixed bed reactors, by 1.0g propylidene acetone self-condensation catalyst (by taking Pd-MgAl-HT as an example) as
One catalyst bed (250 DEG C of bed temperature), 1.5g hydrogenation catalysts are packed into reaction tube as the second catalyst bed 5%Ru/C
In, keep reactor in pressure be 0.6MPa, hydrogen flow rate 150mL/min, by isopropylidene acetone efficient liquid-phase chromatographic pump with
0.05mL/min is pumped into reactor.Reaction result is shown in Table 12.
Influence of 12 different temperatures of table to hydrogenation reaction activity
As can be seen from Table 12, when temperature is in 80-120 DEG C of section, the product of the first bed can be alcohol by complete hydrogenation
Class when temperature is too low or excessively high, is all unable to complete hydrogenation product.
By above example, a series of detailed process (embodiment 1-35) of catalyst preparations is detailed, and to them
The hydrogenation deoxidation reactivity of oxygen-containing presoma in the range of lignocellulosic base gasoline, aviation kerosine comprehensively beg for
By under conditions of given above (embodiment 36-80), obtaining the C of overall yield about 73%12Alkane (product F) yield.
They can be directly used in as novel liquid carbon hydrogen fuel or be made in existing gasoline, aviation kerosine with certain proportion addition
With.On the other hand, the hydrogenation activity for the oxygenatedchemicals (product B, C) that we are also 12 to the carbon chain lengths that the first bed generates
It is explored, under conditions of given above (embodiment 81-97), obtains the C of overall yield about 73%12Alcohol (production
Object C) yield.The C12The raw material of fatty alcohol alcohol (product C) available for synthesising biological matter based surfactants etc..
Liquid fuel produced by the invention can become existing gasoline, the potential substitute of aviation kerosine and biological surface and live
The presoma of property agent.
Claims (6)
1. a kind of preparation method of the branched paraffin in the range of renewable lauryl alcohol and aviation kerosine, it is characterised in that：
It is reacted in the fixed bed flow reactor of the first catalyst bed and the second catalyst bed is filled with successively；
The mixture and hydrogen of one or more of isopropylidene acetone, diacetone alcohol, methyl isobutyl carbinol are in two-bed catalyst
Under the catalysis of agent, lauryl alcohol or carbon chain lengths are directly synthesized as the branched paraffin in the range of 12 aviation kerosine；
1) in the first catalyst bed of fixed bed flow reactor, isopropylidene acetone, diacetone alcohol, methyl isobutyl carbinol
One or more of mixture and hydrogen acid catalyst, base catalyst, metal-doped solid acid catalyst or
Under the catalysis of one or more of metal-doped solid base catalyst, by condensation reaction, it is 12 to obtain carbon number
Oxygen-containing organic compound；
2) on the second catalyst bed of fixed bed flow reactor, the first catalyst bed generation carbon number be 12 it is oxygen-containing
Organic compound and unreacted hydrogen are under metal supported catalyst A/X promotions by the way that hydrogen is added to obtain lauryl alcohol or by adding hydrogen
Deoxidation obtains the branched paraffin in the range of aviation kerosine.
2. preparation method described in accordance with the claim 1, it is characterised in that：
The acid catalyst described in step 1) is one or two or more kinds of mixtures in following solid acids：Acidic resins are (such as：
Amberlyst-15, Amberlyst-16, Amberlyst-36, Amberlyst-45, Amberlyst-70), acidic molecular sieve
(such as：H-ZSM-5, H- β, H-MOR, H-Y etc.), the metal oxide of phosphorylation is (such as：Phosphorylation zirconium oxide, phosphorylation niobium oxide
Deng), acidic metal oxide is (such as：Niobium oxide, tantalum oxide, montmorillonite K-10 or KSF etc.)；
The base catalyst described in step 1) is one or two or more kinds of mixtures in following solid bases：Solid base includes alkali
Property metal oxide is (such as：MgO、CaO、SrO、La2O3、CeO2Deng) alkalinous metal composite oxides are (such as：Magnalium hydrotalcite, lithium aluminium
The KF/Al of hydrotalcite, loading 10-60wt%2O3, Mg/Zr atoms number is than the MgO-ZrO for 1-202Deng), alkaline molecular sieve
(such as：Na-Y, Na-ZSM-5, Na-MOR, Na-MCM-41 etc.), deacidite is (such as：Dowex 1×4、Dowex 1
× 2, Amberlite IRA-900, Amberlite IRA-400 etc.)；
The metal-doped solid acid described in step 1) is cobalt, the above-mentioned solid of nickel, copper, silver, palladium, platinum, ruthenium, iridium, rhodium doping
One or more of acid mixture, the quality doping of doping metals is 0.01-20% in metal-doped solid acid
(preferably 0-5%)；
The metal-doped solid base described in step 1) is cobalt, the above-mentioned solid of nickel, copper, palladium, silver, platinum, ruthenium, iridium, rhodium doping
One or more of alkali mixture, in metal-doped solid base the quality doping of metal for 0.01-20% (preferably
0-5%).
3. preparation method described in accordance with the claim 1, it is characterised in that：
In step 2), using the difunctional A/X types catalyst of load type metal as the second catalyst bed directly to isopropylidene
The condensation reaction products of the mixture of one or more of acetone, diacetone alcohol, methyl isobutyl carbinol carry out plus hydrogen
Or hydrogenation deoxidation；Carrier X is one or two or more kinds of mixtures in following substances：The compound load of activated carbon, silica, sial
Body SiO2-Al2O3(silica alumina ratio is between 0.01-100), molecular sieve are (such as：H-Y, HZSM-5, H β, HMOR etc.), the gold of phosphorylation
Belong to oxide (such as：Phosphorylation zirconium oxide, phosphorylation niobium oxide, phosphorylation tantalum oxide etc.), acidic metal oxide is (such as：Oxidation
Niobium, titanium oxide, tantalum oxide etc.)；Active component A is one or more of Fe, Co, Ni, Cu, Pt, Pd, Ru, Ir, Rh；
Mass fraction 1-50% (preferably 30-50%) of the active component A in catalyst.
4. according to the preparation method described in claim 1,2 or 3, it is characterised in that：
Fixed bed flow reactor dual bed catalyst is used in step 1) and step 2)；Acid catalyst, base catalyst, metal
The solid acid catalyst of doping or metal-doped solid base catalyst are as the first catalyst bed catalysis isopropylidene acetone, double
The condensation reaction of the mixture and hydrogen of one or more of pyruvic alcohol, methyl isobutyl carbinol, highly selective acquisition
Carbon chain lengths are 12 oxygen-containing organic compound；Using load type metal catalyst A/X as the second catalyst bed directly to
The condensation reaction products that one catalyst bed generates carry out plus hydrogen or hydrogenation deoxidation, obtain renewable lauryl alcohol or aviation kerosine model
Enclose branched paraffin；The condition of fixed bed reactors is：First bed catalyst and the second bed catalyst temperature are at 50-500 DEG C
Between (preferably 50-300 DEG C), reaction Hydrogen Vapor Pressure (preferably 0.1-1.0MPa) between 0.1-10.0MPa, the bed of raw material/first
Catalyst quality air speed is in 0.1-10.0h-1(preferably 0.1-5h-1), the bed catalyst mass space velocity of raw material/second is in 0.1-
10.0h-1(preferably 0.1-5h-1), H2Molar ratio with substrate raw material is 1-800 (preferably 1-200).
5. according to the preparation method described in claim 1,2,3 or 4, it is characterised in that：
Carbon number is that 12 oxygen-containing organic compound refers to one in product B, C and its isomer and homologue in table 3
Kind or two kinds or more of mixture；
Product B：
Product C：
Carbon number is that the branched paraffin in the range of 12 aviation kerosine refers to product F and its isomer and homologue in table 10
In one or two or more kinds of mixtures；Product F：
6. according to the method described in claim 1 or 3, it is characterised in that：
Load type metal A/X types catalyst is prepared using incipient impregnation, complexing dipping or deposition sedimentation method,
Equi-volume impregnating process is as follows：First by the soluble salt solutions of A by metering than adding in into the carrier X of advance comprising
Incipient impregnation, stands drying after more than 6h, roasts 2-5h then at 300-700 DEG C (preferably 400-600 DEG C), is made baked
Catalyst；
It is as follows that pickling processes are complexed：The soluble-salt of A is dissolved in equimolar complexing agent first, separately adds water to incipient impregnation,
It is rear dry to stand more than 6h, roasts 2-5h then at 300-700 DEG C (preferably 400-600 DEG C), baked catalyst is made；
Deposition-precipitation method process is as follows：First by the soluble salt solutions of A by metering than adding in hanging to the carrier X of advance comprising
In turbid, it is being stirred continuously the lower corresponding precipitating reagent of addition；And more than aging 2h, filtration drying, then at 300-700 DEG C (preferably
400-600 DEG C) roasting 2-5h, baked catalyst is made.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110079355A (en) * | 2019-04-26 | 2019-08-02 | 中国科学院山西煤炭化学研究所 | A kind of the aviation fuel oil and synthetic method of the synthesis of methyl iso-butyl ketone (MIBK) aldol condensation |
| CN113929559A (en) * | 2021-10-20 | 2022-01-14 | 大连工业大学 | Method for synthesizing branched dodecanol from acetone with high yield |
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| CN103805224A (en) * | 2012-11-06 | 2014-05-21 | 中国科学院大连化学物理研究所 | Preparation method for aviation kerosene |
| CN104711007A (en) * | 2013-12-11 | 2015-06-17 | 中国科学院大连化学物理研究所 | Preparation method of aviation kerosene or diesel oil scope liquid alkane |
| CN108102683A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of preparation method of branched paraffin in the range of renewable lauryl alcohol and aviation kerosine |
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| CN103805224A (en) * | 2012-11-06 | 2014-05-21 | 中国科学院大连化学物理研究所 | Preparation method for aviation kerosene |
| CN104711007A (en) * | 2013-12-11 | 2015-06-17 | 中国科学院大连化学物理研究所 | Preparation method of aviation kerosene or diesel oil scope liquid alkane |
| CN108102683A (en) * | 2016-11-24 | 2018-06-01 | 中国科学院大连化学物理研究所 | A kind of preparation method of branched paraffin in the range of renewable lauryl alcohol and aviation kerosine |
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| CN110079355A (en) * | 2019-04-26 | 2019-08-02 | 中国科学院山西煤炭化学研究所 | A kind of the aviation fuel oil and synthetic method of the synthesis of methyl iso-butyl ketone (MIBK) aldol condensation |
| CN110079355B (en) * | 2019-04-26 | 2020-08-04 | 中国科学院山西煤炭化学研究所 | Aviation fuel oil synthesized by methyl isobutyl ketone aldol condensation and synthesis method |
| CN113929559A (en) * | 2021-10-20 | 2022-01-14 | 大连工业大学 | Method for synthesizing branched dodecanol from acetone with high yield |
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