Preparation method of reproducible dodecanol and branched paraffin in range of aviation kerosene

Abstract

The invention relates to a preparation method of biomass-based dodecanol and branched paraffin in a range of aviation kerosene. The preparation method comprises two parts: 1), mesityl oxide, diacetonealcohol and methyl isobutyl carbinol or a mixture of two or more of the compounds is subjected to a condensation reaction on a first catalyst bed layer of a fixed bed continuous reactor under catalysis of an acid catalyst, a base catalyst, a metal doped solid acid catalyst or a metal doped solid base catalyst, and an oxygen-containing organic compound with carbon chain length being 12 is obtained; 2), a condensation product produced on the first catalyst bed layer and unreacted hydrogen are subjected to a hydrogenation reaction on a second catalyst bed layer of the fixed bed continuous reactor at lower reaction temperature under the acceleration of a metal catalyst, and dodecanol is obtained.

Description

technical field

[0001] The present invention relates to a kind of preparation method of branched alkanes within the range of renewable dodecanol and aviation kerosene, which specifically comprises two steps: 1) in the first catalyst bed layer of fixed bed continuous reactor, lignocellulosic biomass platform Compound mesityl oxide, diacetone alcohol, methyl isobutyl carbinol or a mixture of two or more of these compounds with hydrogen in an acid catalyst, base catalyst, metal-doped solid acid catalyst or metal-doped Under the promotion of a solid base catalyst, an oxygen-containing organic compound with a carbon chain length of 12 is obtained through a condensation reaction; 2) On the second catalyst bed of the fixed-bed continuous reactor, the first catalyst bed generates a carbon chain length of 12 The oxygenated organic compounds can be hydrogenated or hydrodeoxygenated under the promotion of supported metal A / X type bifunctional catalysts to obtain renewable dodecanol or br...

Examples

Embodiment 1-14

[0028] 1. Preparation of catalyst:

[0029] 1) Preparation of solid acid catalysts: Nafion and Amberlyst resins, Y-type molecular sieves, montmorillonite K-10 and KSF are commercial catalyst products purchased directly.

[0030] Phosphorylated zirconium oxide (ZrP) catalyst is mixed with 1mol / L zirconium oxychloride and ammonium dihydrogen phosphate aqueous solution at a volume ratio of 2:1, and the obtained precipitate is washed and filtered repeatedly, dried at 120°C for 10 hours, and then placed in Calcined at 400°C for 4h.

[0031] 2) Preparation of solid base catalysts: Alkaline earth oxides (MgO, CaO, SrO) and rare earth oxides (La2O3, CeO2) were obtained by calcining the corresponding nitrates under N2 atmosphere for 8h, respectively.

[0032] Magnesium-aluminum hydrotalcite is to dissolve 0.093mol Mg(NO3)2·6H2O and 0.0465molAl(NO3)3·9H2O in 100ml of water, add 0.219mol NaOH and 0.0565mol Na2CO3 to the solution in a water bath at 70°C in 100ml of aqueous solution dropw...

Embodiment 13

[0043] Sedimentation and precipitation method: Prepare 0.0175M nickel nitrate solution and divide it into two parts A and B in equal volume. Add silica, H-ZSM-5, H-MOR, silicon-aluminum composite carrier, H-β molecular sieve, oxidation One kind of aluminum and an appropriate amount of concentrated nitric acid, 0.0525M urea was added to B, B was slowly added dropwise to A in a water bath at 80°C, the temperature was raised to 90°C, stirred for 10 hours, filtered and washed, dried overnight at 80°C, and air roasted at 500°C for 2 hours. The calcined catalyst was reduced in situ with hydrogen at 500 °C for 2 h in a fixed bed. (see table 1, embodiment 14-18)

Embodiment 14-18

[0044] Table 1 Supported metal A / X type bifunctional catalyst

[0045]

[0046]

[0047] 2 Self-condensation reaction: In a fixed-bed reactor, put 1.0g of catalyst into the reaction tube, keep the hydrogen pressure in the reactor at 0.6MPa, and the hydrogen flow rate at 150mL / min. mL / min was pumped into the reactor. The reaction results are shown in Table 2 and Table 3.

[0048] Table 2 Propylene oxide self-condensation reaction result

[0049]

[0050] As can be seen from Table 2, solid acid and basic catalysts without metal doping are not ideal for the self-polymerization reaction of propylene glycol. When doping noble metals on acid or base catalysts (Example 19-35), dodecyl ketones and alcohols can be generated. Among them, the activity is better when the magnesium aluminum hydrotalcite doped with Pd.

[0051] Table 3 Self-condensation reaction target product structural formula

[0052]

technical field

[0001] The present invention relates to a kind of preparation method of branched alkanes within the range of renewable dodecanol and aviation kerosene, which specifically comprises two steps: 1) in the first catalyst bed layer of fixed bed continuous reactor, lignocellulosic biomass platform Compound mesityl oxide, diacetone alcohol, methyl isobutyl carbinol or a mixture of two or more of these compounds with hydrogen in an acid catalyst, base catalyst, metal-doped solid acid catalyst or metal-doped Under the promotion of a solid base catalyst, an oxygen-containing organic compound with a carbon chain length of 12 is obtained through a condensation reaction; 2) On the second catalyst bed of the fixed-bed continuous reactor, the first catalyst bed generates a carbon chain length of 12 The oxygenated organic compounds can be hydrogenated or hydrodeoxygenated under the promotion of supported metal A / X type bifunctional catalysts to obtain renewable dodecanol or br...

Examples

Embodiment 1-14

[0028] 1. Preparation of catalyst:

[0029] 1) Preparation of solid acid catalysts: Nafion and Amberlyst resins, Y-type molecular sieves, montmorillonite K-10 and KSF are commercial catalyst products purchased directly.

[0030] Phosphorylated zirconium oxide (ZrP) catalyst is mixed with 1mol / L zirconium oxychloride and ammonium dihydrogen phosphate aqueous solution at a volume ratio of 2:1, and the obtained precipitate is washed and filtered repeatedly, dried at 120°C for 10 hours, and then placed in Calcined at 400°C for 4h.

[0031] 2) Preparation of solid base catalysts: Alkaline earth oxides (MgO, CaO, SrO) and rare earth oxides (La2O3, CeO2) were obtained by calcining the corresponding nitrates under N2 atmosphere for 8h, respectively.

[0032] Magnesium-aluminum hydrotalcite is to dissolve 0.093mol Mg(NO3)2·6H2O and 0.0465molAl(NO3)3·9H2O in 100ml of water, add 0.219mol NaOH and 0.0565mol Na2CO3 to the solution in a water bath at 70°C in 100ml of aqueous solution dropw...

Embodiment 13

[0043] Sedimentation and precipitation method: Prepare 0.0175M nickel nitrate solution and divide it into two parts A and B in equal volume. Add silica, H-ZSM-5, H-MOR, silicon-aluminum composite carrier, H-β molecular sieve, oxidation One kind of aluminum and an appropriate amount of concentrated nitric acid, 0.0525M urea was added to B, B was slowly added dropwise to A in a water bath at 80°C, the temperature was raised to 90°C, stirred for 10 hours, filtered and washed, dried overnight at 80°C, and air roasted at 500°C for 2 hours. The calcined catalyst was reduced in situ with hydrogen at 500 °C for 2 h in a fixed bed. (see table 1, embodiment 14-18)

Embodiment 14-18

[0044] Table 1 Supported metal A / X type bifunctional catalyst

[0045]

[0046]

[0047] 2 Self-condensation reaction: In a fixed-bed reactor, put 1.0g of catalyst into the reaction tube, keep the hydrogen pressure in the reactor at 0.6MPa, and the hydrogen flow rate at 150mL / min. mL / min was pumped into the reactor. The reaction results are shown in Table 2 and Table 3.

[0048] Table 2 Propylene oxide self-condensation reaction result

[0049]

[0050] As can be seen from Table 2, solid acid and basic catalysts without metal doping are not ideal for the self-polymerization reaction of propylene glycol. When doping noble metals on acid or base catalysts (Example 19-35), dodecyl ketones and alcohols can be generated. Among them, the activity is better when the magnesium aluminum hydrotalcite doped with Pd.

[0051] Table 3 Self-condensation reaction target product structural formula

[0052]

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