Iron-based composite catalyst for on-line upgrading of bio-oil and its preparation and application method

A composite catalyst, bio-oil technology, applied in chemical instruments and methods, preparation of liquid hydrocarbon mixtures, catalysts for physical/chemical processes, etc., can solve the problems of easy sintering deactivation, low catalytic activity, easy carbon deposition deactivation, etc. Achieve the effect of preventing catalyst deactivation, improving catalytic activity, and increasing calorific value

Active Publication Date: 2018-08-31
ENERGY RES INST OF SHANDONG ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Among them, metal oxide raw materials are easy to obtain and low in price, but their catalytic activity is low; noble metal catalysts have high activity, but are expensive and are prone to sintering deactivation under high temperature conditions or long-term operation; molecular sieve catalysts can meet high The two functions of activity and shape-selective catalysis, but because of its strong acidity, it is easy to deactivate due to carbon deposition

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Embodiment 1: a kind of preparation method of iron-based composite catalyst, it comprises the steps:

[0028] Preparation of LDHs precursors: according to Mg 2+ : Ca 2+ : Fe 3+ :Al 3+ Weigh 48.10g Mg(NO 3 ) 2 ∙6H 2 O, 44.27g Ca(NO 3 ) 2 ∙6H 2 O, 75.50g Fe(NO 3 ) 3 ∙9H 2 O and 70.89g Al(NO 3 )2 ∙9H 2 O was added to deionized water to form a 500 ml mixed solution, and 50.99g NaNO was weighed 3 Add deionized water to prepare a 500 ml mixed solution, and weigh 56g NaOH and add deionized water to prepare an 800 mL alkali solution with a concentration of 2M. NaNO 3 Pour the solution and NaOH solution into a four-necked flask, add the mixed salt solution dropwise to the above mixed alkali solution under mechanical stirring, so that the pH of the final solution is 11.2, crystallize the resulting slurry at room temperature for 24 hours, and use deionized water Wash and centrifuge 4 times, dry at 100°C for 12 hours, and grind to obtain the LDHs precursor.

[0029...

Embodiment 2

[0035] The preparation method of the catalyst in this embodiment is the same as that of Example 1 and will not be repeated, the difference is that the active component content is different, wherein Mg 2+ : Ca 2+ : Fe 3+ :Al 3+ The molar ratio is about 4:4:1:1. The composition and mass percentage of the prepared catalyst were Fe: 11.41%, CaO: 42.06%, Mg(Al)O: 46.53%, and no other impurity phases were found, and the average size of Fe nanoparticles was 5.2 nm.

[0036] On-line upgrading of the crude bio-oil product was performed under the same cracking conditions as in Example 1. Experimental research found that compared with the crude product of bio-oil, the acidic substances in the refined bio-oil were completely removed, the content of aldehydes and ketones was reduced to 5.46%, and the content of hydrocarbons increased to 33.52% (the content of aliphatic hydrocarbons was 18.89%, the content of aromatic hydrocarbons is 14.63%), the content of phenolic compounds slightly i...

Embodiment 3

[0038] The composition and mass percentage of the catalyst in this example are consistent with Example 1, being Fe: 27.78%, CaO: 28.06%, Mg(Al)O: 44.16%, no other impurity phases are found, and the average size of Fe nanoparticles 7.3nm. The preparation method is the same as in Example 1, and will not be repeated here.

[0039] The application method of using the above-mentioned iron-based composite catalyst for bio-oil online upgrading is the same as Example 1 and will not be repeated. The difference from Example 1 is that the catalyst and wood powder are loaded in different ways during the bio-oil upgrading process. Specifically In order to put 0.5mg of wood powder and 10mg of catalyst into the sample tube and shake them to mix them evenly. Experimental research found that the content of acidic substances in the upgraded bio-oil was 16.18%, the content of hydrocarbons was 20.58% (of which the content of aliphatic hydrocarbons was 4.32%, the content of aromatic hydrocarbons ...

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Abstract

The invention discloses a method for improving quality of bio-oil online by utilizing an iron-based composite catalyst. The method is characterized by comprising the following steps of by taking Fe / CaO / Mg(Al)O as a catalyst and wood flour as a biomass raw material, filling the biomass and the catalyst in a reactor for rapid pyrolysis, directly performing catalytic cracking on steam produced by biomass pyrolysis on the surface of the catalyst, acquiring bio-oil steam after quality improvement, and finally, performing GC / MS online component and content analysis on the bio-oil steam after qualityimprovement, wherein the catalyst takes Mg(Al)O as a carrier, Fe as a steam conversion main active component and CaO as a cocatalyst component and a carrier, and the mass percentages of various components are as follows: the mass percentage of Fe is 10-30 percent, the mass percentage of CaO is 25-48 percent, and the mass percentage of Mg(Al)O is 40-48 percent.

Description

technical field [0001] The invention belongs to the technical field of utilization of biomass energy, and more specifically relates to an Fe-based composite catalyst for on-line upgrading of bio-oil and its preparation and application method. Background technique [0002] As a renewable clean energy, bio-oil, a liquid product obtained through rapid pyrolysis and liquefaction of biomass, is a new type of liquid fuel, which has the advantages of high energy density, easy storage and transportation, and low sulfur and nitrogen content. It is hoped to alleviate the environmental pollution problems caused by energy shortage and the use of fossil fuels. However, the composition of the crude bio-oil product is very complex, including almost all kinds of oxygen-containing organic compounds (acids, aldehydes, ketones, alcohols, phenols, furans, sugars, etc.), resulting in poor stability, high acidity, low calorific value, high viscosity, etc. The disadvantages have seriously hindere...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/78C10G1/00
CPCB01J23/007B01J23/78B01J35/006B01J35/0093C10G1/00C10G1/002C10G2300/1014
Inventor 杨双霞张晓东陈雷孙来芝谢新苹司洪宇
Owner ENERGY RES INST OF SHANDONG ACAD OF SCI
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