A kind of preparation method for the catalyst of bio-oil hydrodeoxygenation

A hydrodeoxygenation and catalyst technology, which is used in metal/metal oxide/metal hydroxide catalysts, preparation of liquid hydrocarbon mixtures, physical/chemical process catalysts, etc., can solve the problem that bio-oil cannot meet clean fuel quality standards, metal The problems of low content of nickel and tungsten trioxide, reducing the activity of amorphous catalysts, etc., can achieve the effect of excellent catalytic activity, high-quality deoxidation, and reducing the content of benzene or aromatics.

Inactive Publication Date: 2015-09-09
XIANGTAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

But because of the preparation process NaBH 4 The slow drop rate of the solution makes it easy to undergo rapid oxidation and decomposition, resulting in a large amount of boron oxides accumulating on the surface of the catalyst, and part of the catalytic active center is covered, resulting in a very low content of metallic nickel and tungsten trioxide on the surface of the catalyst, thus Significantly reduce the activity of Ni–W–B amorphous catalyst, and make the catalyst produce a certain amount of benzene or aromatic products in the reaction of catalyzed aromatic ring oxygenates in bio-oil. The bio-oil after deoxygenation still cannot meet the requirements of clean fuel oil. quality standard

Method used

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  • A kind of preparation method for the catalyst of bio-oil hydrodeoxygenation
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  • A kind of preparation method for the catalyst of bio-oil hydrodeoxygenation

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] 1.31 g NiSO 4 ·6H 2 O was dissolved in 25 mL of water, and 2.5 g of 25% NH 3 ·H 2 O, add 1.65 g Na 2 WO 4 2H 2 O, stirred and dissolved, transferred to a 250 mL three-necked flask, and then added 25 mL of 1.0 mol / mL NaBH 4 solution, at 30°C under vigorous stirring, add 1 mL of 0.001 mol / / mL of Ag + solution, the reaction occurred immediately, and a black precipitate was obtained after the reaction, washed with water and alcohol, and dried in a vacuum oven at 40°C for 5 hours.

[0027] Add 88.24 g of n-dodecane, 11.76 g of phenol and 0.20 g of the catalyst prepared above in the autoclave, install the device, remove the air in the autoclave, then rise from room temperature to 225 °C at a rate of 10 °C / min, adjust The rotation speed was 900 r / min, the hydrogen pressure was 4.0 MPa, and the reaction was continued for 3 h. The product was analyzed by Agilent 6890 / 5973N GC / MS. The conversion rate of phenol reaches 100%, and the selectivity of cyclohexane reaches 79.6%...

Embodiment 2

[0029] 1.18 g NiCl 2 ·6H 2 O was dissolved in 25 mL of water, and 2.5 g of 25% NH 3 ·H 2 O, add 1.65 g Na 2 WO 4 2H 2 O, stirred and dissolved, transferred to a 250 mL three-necked flask, and then added 25 mL of 1.0 mol / mL NaBH 4 solution, at 30°C under vigorous stirring, add 1 mL of 0.001 mol / / mL of Ag + solution, the reaction occurred immediately, and a black precipitate was obtained after the reaction, washed with water and alcohol, and dried in a vacuum oven at 40°C for 5 hours.

[0030] Add 88.24g of n-dodecane, 11.76g of phenol and 0.20g of the catalyst prepared above in the autoclave, install the device, remove the air in the kettle, then rise from room temperature to 225°C at a rate of 10°C / min, adjust The rotation speed was 900 r / min, the hydrogen pressure was 4.0 MPa, and the reaction was continued for 3 hours. The product was analyzed by Agilent 6890 / 5973N GC / MS. The conversion rate of phenol was 100%, and the selectivity of cyclohexane was 71.8%.

Embodiment 3

[0032] 0.59 g NiCl 2 ·6H 2 O was dissolved in 25 mL of water, and 2.5 g of 25% NH 3 ·H 2 O, add 1.65 g Na 2 WO 4 2H 2 O, stirred and dissolved, transferred to a 250 mL three-necked flask, and then added 25 mL of 1.0 mol / mL NaBH 4 solution, at 30 ℃ and vigorously stirred, add 1 mL of 0.001 mol / / mL of Ag + solution, the reaction occurred immediately, and a black precipitate was obtained after the reaction, washed with water and alcohol, and dried in a vacuum oven at 40°C for 5 hours.

[0033] Add 88.24 g of n-dodecane, 11.76 g of phenol and 0.20 g of the catalyst prepared above in the autoclave, install the device, remove the air in the autoclave, then rise from room temperature to 225 °C at a rate of 10 °C / min, adjust The rotation speed was 900 r / min, the hydrogen pressure was 4.0 MPa, and the reaction was continued for 3 hours. The product was analyzed by Agilent 6890 / 5973N GC / MS. The conversion rate of phenol reaches 100%, and the selectivity of cyclohexane reaches 86...

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Abstract

The invention discloses a preparation method of an amorphous catalyst for catalytic hydrodeoxygenation of phenol, aldehyde, alcohol and ketone oxygenated compounds in biological oil. The catalyst mainly consists of Ni, W and B as active ingredients. The preparation method comprises a step of preparing the catalyst through induced chemical deposition by taking soluble nickel salt and tungstate as raw materials, NaBH4 or KBH4 as a reducing agent and ammonia water or ethidene diamine as a chelating agent. The preparation method has the characteristics of improving utilization rate of the NaBH4 or KBH4 as a reducing agent, reducing coverage of boron oxide in active centers on the surface of the catalyst, and increasing the number of the active centers on the surface of the catalyst; the entire preparation method is simple in process, moderate in preparation condition and free from protective gas; the prepared catalyst is quite high in catalysis activity, and can implement catalytic hydrodeoxygenation of the oxygenated compounds at relatively low reaction temperature and obviously reduce contents of benzene of aromatic hydrocarbon in a reaction product.

Description

technical field [0001] The invention belongs to the technical field of oil refining, and in particular relates to a method for preparing a catalyst for hydrodeoxygenation of bio-oil. Background technique [0002] With the continuous depletion of fossil energy reserves, mankind is facing an energy crisis, which has led to fierce competition for oil resources and a sharp rise in oil prices. As a renewable energy source, bio-oil has been recognized as the most potential and ideal substitute for fossil energy in the world. However, bio-oil contains a large amount of oxygen-containing compounds such as phenols, aldehydes, alcohols and ketones, etc., and the oxygen content in it is as high as 40%, resulting in low combustion value of bio-oil, poor chemical stability, and corrosion to equipment. However, the disadvantages such as non-resistance seriously affect the wide use of bio-oil as hydrocarbon fuel. Therefore, it is necessary to refine the oxygenated compounds in bio-oil by...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/888C10G3/00
CPCY02P30/20
Inventor 王威燕杨运泉张锟刘文英乔志强仵奎
Owner XIANGTAN UNIV
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