Method for improving quality of phenolic materials in tar

A technology of tar and phenol series, which is applied in the field of phenol series in tar oil to improve the quality, can solve the problems of increasing the difficulty of the separation process and the limited reduction of tar acidity, and achieve the effect of reducing acidity and polarity and increasing calorific value

Active Publication Date: 2017-07-14
INST OF PROCESS ENG CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, due to the presence of more alkylphenols in addition to aromatic ethers in the resulting oil, the reduction in acidity of tar is limited, and the product also contains a certain amount of aromatics and chains in addition to aromatic ethers and alkylphenols. Hydrocarbons and other products increase the difficulty of the subsequent separation process

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] A method for improving the quality of phenols in tar oil, the method comprising the following steps:

[0046] (1) The tar obtained by pyrolyzing the fuel ethanol fermentation residue at 550℃ (the content of phenol series is 88%, the molar ratio of alkylphenol to alkoxyphenol is about 1.2:1) is mixed with methanol (mass ratio 1:1) , With 20g of alkali metal salt or alkali metal oxide modified solid acid as catalyst, the first-stage reaction is carried out at 420℃ for 2h, and the gas phase mass space velocity of the catalyst bed is 0.01h -1 , Get the first-level product;

[0047] (2) Mix the first-stage product obtained in step (1) with methanol (mass ratio 1:1), use alkali metal salt or alkali metal oxide modified solid acid as a catalyst, and carry out the second-stage reaction at 450°C 2h, the gas phase mass space velocity of the catalyst bed is 6h -1 , Get the second grade product.

[0048] Wherein, the catalyst in step (1) is made of KNO 3 Potassium oxide modified γ-Al obt...

Embodiment 2

[0052] A method for improving the quality of phenols in tar oil, the method comprising the following steps:

[0053] (1) Creosote oil obtained by cutting Liulin coal tar from pyrolysis at 650°C (92% phenolic content, in which the molar ratio of alkylphenol to alkoxyphenol is about 1.5:1) and methanol (mass ratio 1:3) Mix, take 20g of alkali metal salt or alkali metal oxide modified solid acid as catalyst, carry out the first-stage reaction at 450℃ for 2h, the gas phase mass space velocity of the catalyst bed is 1.4h -1 , Get the first-level product;

[0054] (2) Mix the first-stage product obtained in step (1) with methanol (mass ratio 1:1), use alkali metal salt or alkali metal oxide modified solid acid as a catalyst, and perform the second-stage reaction at 430°C 2h, the gas phase mass space velocity of the catalyst bed is 4.6h -1 , Get the second grade product.

[0055] Wherein, the catalyst in step (1) is made of K 2 CO 3 The potassium oxide modified ZSM-5 catalyst (alkali metal...

Embodiment 3

[0059] A method for improving the quality of phenols in tar oil, the method comprising the following steps:

[0060] (1) The tar obtained from the pyrolysis of pine wood powder at 500℃ (the content of phenol series is 72%, the molar ratio of alkylphenol to alkoxyphenol is about 1:1.2) is mixed with methanol (mass ratio 1:3), and 20g The solid acid modified by alkali metal salt or alkali metal oxide is used as the catalyst. The first-stage reaction is carried out at 470℃ for 2h, and the gas phase mass space velocity of the catalyst bed is 2.2h -1 , Get the first-level product;

[0061] (2) Mix the first-stage product obtained in step (1) with methanol (mass ratio 1:2), use alkali metal salt or alkali metal oxide modified solid acid as a catalyst, and carry out the second-stage reaction at 400°C 2h, the gas phase mass space velocity of the catalyst bed is 2h -1 , Get the second grade product.

[0062] Wherein, the catalyst in step (1) is made of NaNO 3 The sodium oxide modified MCM-41...

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PUM

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Abstract

The invention provides a method for improving quality of phenolic materials in tar. The method is characterized by finally converting the phenolic materials into aromatic ethers through a two-stage conversion process. The method comprises the following steps: firstly mixing the tar with alkylation reagents and carrying out first-stage reaction under the action of a solid acid catalyst modified by alkali metal salt or alkali metal oxide to obtain a first-stage product; mixing the first-stage product or alkylphenol obtained by separating the first-stage product with the alkylation reagents, and carrying out second-stage reaction by taking solid acid modified by alkali metal salt or alkali metal oxide as a catalyst to obtain a second-stage product. Through the method, the phenolic materials are converted into the aromatic ethers, the heat value and oil-phase solubility of the tar and/or creosote oil can be effectively improved; the acidity and the corrosivity of the tar and/or the creosote oil can be reduced; the quality of the tar and/or the creosote oil is improved; the process is simple and efficient; the costs of raw materials are low; the operation cost is low; the industrial production is easy to implement; the raw materials used by the method are pollution-free; the treatment process is pollution-free; the method is an environment-friendly green process.

Description

Technical field [0001] The invention belongs to the field of tar treatment, and relates to a method for upgrading tar oil, in particular to a method for upgrading phenolic compounds in tar oil. Background technique [0002] Tar is a black or dark brown viscous liquid obtained during the dry distillation of coal or biomass. It has a special odor, is combustible and corrosive. It is a complex mixture of hydrocarbons with high aromaticity. Cheap fuel sources and precious chemical resources. However, tar, especially low-temperature pyrolysis tar, is rich in creosote components containing a large number of oxygen atoms, resulting in low calorific value and high acidity of tar, which limits its direct application as a liquid fuel, so it must be refined to reduce It is acidic and increases calorific value. [0003] At present, the main tar upgrading programs include component distillation separation technology for component separation, tar catalytic hydrogenation, and catalytic cracking...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C10C1/20
CPCC10C1/20
Inventor 王泽张少华宋文立林伟刚李松庚
Owner INST OF PROCESS ENG CHINESE ACAD OF SCI
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