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Supported catalyst for hydrogenation of alpha-pinene and preparation method and uses thereof

A catalyst and supported technology, applied in the chemical industry, can solve the problems of low cis-trans of pinane, difficult to improve product quality, harsh reaction conditions, etc.

Inactive Publication Date: 2013-05-15
KUNMING UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

If the cis-isomer content in the pinane raw material is too low and the trans-isomer content is too high, there will be more by-products in the subsequent reaction, and the main product yield will decrease
The product is also difficult to separate and purify, and the product quality is difficult to improve
[0003] Among the currently used catalysts for hydrogenating α-pinene to produce cis-pinane, supported palladium, platinum, rhodium and other noble metal catalysts have higher α-pinene hydrogenation activity, but the cost is high, and the pinane in the product low cis-trans ratio
Supported Ni-based catalysts have better activity and selectivity under certain reaction conditions, but the reaction conditions are harsh and the reaction time is longer

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0031] Example 1 In the nickel chloride aqueous solution with a concentration of 0.1mol / L, molecular sieves were added according to the nickel salt load as 4% mass fraction, fully stirred, and dried at 90°C for 20 hours after immersion for 8 hours; the dried mixture was placed at 200 Roast at ℃ for 3 hours, add appropriate amount of potassium hydroxide to the potassium borohydride solution with a concentration of 0.1mol / L, adjust to pH = 9; put the above potassium borohydride solution in a water bath at 20℃, press Ni:B =1:1 molar ratio Add the above roasted mixture, stir for 15min, filter and wash once with a certain amount of ammonia water, wash three times with distilled water, and wash twice with absolute ethanol.

[0032] The amount of catalyst used is 3% of the quality of α-pinene, α-pinene and catalyst are placed in the reaction kettle, vacuumized for ten minutes at a gauge pressure of 0.06MPa, replaced three times with nitrogen at 0.4MPa, and then hydrogen is used to Re...

Embodiment 2

[0035] Example 2 In the nickel chloride aqueous solution with a concentration of 0.5 mol / L, molecular sieves were added according to the nickel salt load as 12% mass fraction, fully stirred, and dried at 110°C for 12 hours after immersion for 12 hours; the dried mixture was dried at 250 Roast at ℃ for 2 hours, add appropriate amount of potassium hydroxide to the potassium borohydride solution with a concentration of 0.5mol / L, adjust to pH = 11; put the above potassium borohydride solution in a water bath at 0℃, press Ni:B =1:2 molar ratio Add the above roasted mixture, stir for 15min, filter and wash once with a certain amount of ammonia water, wash three times with distilled water, and wash twice with absolute ethanol.

[0036] According to the amount of catalyst used is 1.6% of the mass of α-pinene, α-pinene and catalyst are placed in the reaction kettle, vacuumized for ten minutes at a gauge pressure of 0.07MPa, replaced with nitrogen four times at 0.2MPa, and then hydrogen ...

Embodiment 3

[0039] Example 3 In the nickel chloride aqueous solution with a concentration of 1 mol / L, molecular sieves were added according to the nickel salt load of 20% mass fraction, fully stirred, and dried at 130°C for 20h after immersion for 24h; the dried mixture was dried at 350°C Roasting at lower temperature for 1h, add an appropriate amount of potassium hydroxide to the potassium borohydride solution with a concentration of 1mol / L to adjust to pH = 13; put the above potassium borohydride solution in a water bath at 40°C, and press Ni:B=1 after constant temperature : 3 molar ratio, add the above-mentioned roasted mixture, stir for 15min, wash once with a certain amount of ammonia water after filtering, wash three times with distilled water, and wash twice with absolute ethanol.

[0040] The amount of catalyst used is 0.2% of the mass of α-pinene, α-pinene and catalyst are placed in the reaction kettle, vacuumized for ten minutes at a gauge pressure of 0.08MPa, replaced three time...

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PUM

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Abstract

The invention relates to an amorphous catalyst, and a preparation method and uses thereof. The catalyst is Ni-B-molecular sieve supported amorphous catalyst, and the preparation method comprises the steps of: based on 1 to 30% of the supported amount of nickel salt by mass fraction, adding a molecular sieve to nickel chloride aqueous solution with the concentration of 0.1 to 1mol / L, sufficiently stirring, impregnating for 4 to 24 hours and then drying for 4 to 20 hours at 50 to 130 DEG C; roasting the dried mixture for 1 to 3 hours at 200 to 600 DEG C, adding appropriate amount of potassium hydroxide to potassium borohydride solution with the concentration of 0.1 to 1mol / L, adjusting pH to the range from 9 to 13; putting the potassium borohydride solution in water bath with the temperature ranging from 0 to 80 DEG C, adding the roasted mixture at constant temperature based on the molar ratio of Ni:B = 1:1 to 3, stirring the solution for 15 minutes, filtering and then washing once withfixed amount of ammonia water, washing three times with distilled water, then washing twice with absolute ethyl alcohol, and sealing with alcohol for future use. The catalyst of the invention is usedfor catalyzing the hydrogenation reaction of alpha-pinene, and has the advantages of short technological flow, low reaction temperature, lowered energy consumption, small using amount of catalyst, high cis-pinane yield and good selectivity.

Description

technical field [0001] The invention belongs to the field of chemical industry and relates to a supported amorphous catalyst used for hydrogenating alpha-pinene to prepare cis-pinane. Background technique [0002] α-pinene is the main component of turpentine. Turpentine is a natural essential oil obtained from Pinaceae plants. It has the largest output in nature and the cheapest price. At present, the main way to produce pinane in industry is to prepare it by catalytic hydrogenation of α-pinene. Cis-pinane is an important raw material for the perfume and pharmaceutical industry and other pinene deep-processing industries, especially for the preparation of dihydromyrcenol, linalool and other perfumes. The pinane used in the perfume industry is required to be mainly in the cis form, because the reactivity of the cis form is higher than that of the trans form. If the cis-isomer content in the pinane raw material is too low and the trans-isomer content is too high, there will ...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J29/00C07C13/39C07C5/03
Inventor 蒋丽红王昊王亚明苗雨欣贾庆明陕绍云
Owner KUNMING UNIV OF SCI & TECH