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How catalysis helps to advance bioenergetics

1 October 2021

Obtaining different biofuels and their integration into the traditional oil processing is a promising direction of the “green” energetics. At Ruscatalysis-2021 Congress Dr. Vadim Yakovlev, head of the Engineering Center of Boreskov Institute of Catalysis, spoke on the technologies of biomass processing and the ways of improving the quality of such fuels.

How biofuel is produced

The volume of biomass available for processing exceeds the existing energy consumption of all of humankind three times, 46 terawatt against 14 terawatt. In Russia the technical potential of processing is five times higher than the volume of the consumed power, and in terms of economy the expedient potential is about 10% of the level of today’s consumption.

According to Vadim Yakovlev, the technologies of bioenergetics can be divided into three directions.

“The first is a biochemical way, obtaining of bio-alcohols. The second is a thermochemical way including gasification, pyrolysis of lignocellulose with further production of bio-oil and energy carriers. And there is also an oleochemical way, i.e. processing of lipids for producing bio-diesel and “green” diesel and jet fuel”, he said.

The technology of bio-alcohol synthesis uses a fast-growing biomass, such as miscanthus, from which first lignocellulose pulp is produced, and then the sugars are hydrolyzed followed by fermentation to ethanol.

Upon thermal processing of biomass in case of slow pyrolysis the main product is biochar, i.e. charcoal, and if the biomass particles are heated fast, and the products of lignocellulose depolymerization are cooled fast, then mainly liquid compounds would be obtained.

With the help of gasification the biomass is used to produce synthesis gas which can be further used in the Fischer-Tropsch processes for obtaining liquid hydrocarbons. The so produced fuel has a higher cetane rating and low sulfur content. Also synthesis gas can be used to produce methanol. This is a cheap alcohol for manufacturing of many useful compounds – dimethyl ether, components of fuel elements, hydrogen, and bio-diesel.

Processing of bio-oil and its place in the consolidated power generation cycle

Biological types of fuel are added to the traditional ones, which improves the quality of the fuel as well as provides economical preferences. Today the processes of obtaining of bio-gas and other fuels through the Fischer-Tropsch reaction have high capital expenditures that significantly exceed the prime cost of producing common petroleum. The problem of manufacturing bio-diesel is expensive material. According to Yakovlev, this is a flattering background for pyrolysis technologies of producing bio-oil with further hydroprocessing.

“The ablation reactors for quick pyrolysis provide an immediate contact of chopped biomass with heated surface. The heat transfer here is orders of magnitude higher than that with usual convective or infrared radiation. The biomass particles begin to heat quickly and decompose. Then the products of thermolysis of biomass should be cooled fast so that it would not decompose further to carbon dioxide and water”, the scientist explained the process.

Bio-oil is a complex mixture of oxygen-containing compounds from light alcohols, ethers, acids, aldehydes to phenolic products. It contains a lot of oxygen, and this causes difficulties for further processing and use. The fuel has a number of disadvantages – increased viscosity, high acidity due to carbon acids, and, as a result, thermal and chemical instability as well as a tendency for repolymerization, asphaltization, and coke-formation. In addition bio-oil is polar, whereas the traditional oil is not, and the joint processing along with usual oil becomes a problem to be solved.

The international consortium of academic and industrial organizations formed within the international FP-8 and 7 programs suggest the following approach. Biomass is subjected to quick pyrolysis in its habitats, and thus bio-oil is produced. The productivity of such plants is 1.5-2 tons per hour, it is not very much, but it is justified in terms of logistics. Then bio-oil is transported to an oil-processing plant, where it undergoes soft hydroprocessing in the course of which oxygen is partially removed, which makes the mixture more stable. Due to this no intensive asphaltization occurs at the following stages with higher temperature of processing. And this product can be delicately integrated into the existing processes of oil processing.

The catalysts for hydroprocessing must be resistant to acidic medium, hydrothermal impact, and coke-formation. The scientists developed the catalytic systems that meet these criteria.

“We modified the nickel-containing catalysts with phosphorus and molybdenum, and the testing at the pilot plants showed that coke-formation and maceration of metals decreased significantly, which allowed increasing the resource of the catalyst several times”, noted Vadim Yakovlev.

Speaking about the joint processing of oil with bio-additives, the catalytic cracking allows using the vegetative oxygenates without limitation. The vegetative oxygenates can be only partially (no more than 5% in the mixture) integrated into the hydrotreating, and the joint reforming is impossible with the use of the existing catalysts of reforming. However, the researchers of the Center of New Chemical Technologies of Boreskov Institute of Catalysis presented at the Congress their very interesting work on fluoridated catalysts of reforming that can turn out to be more stable in the processes of the joint processing of oil products and vegetative oxygenates.

Obtaining biofuels from vegetative lipids 

Bio-diesel is produced from vegetative oils by inter-esterification with methanol. There are heterogeneous and homogeneous approaches to the process. The homogeneous approach involves alkali or methylates of alkali metals as catalysts. This technology is simple, but a problem arises concerning processing of glycerin that is contaminated by the products of alkali neutralizations. The technologies with the use of heterogeneous catalysts require high temperatures and pressures, but the obtained products feature the required purity.

According to Yakovlev, there are single examples of heterogeneous approach to producing bio-diesel. For instance, two consequent reactors are engaged with intermediate isolation of glycerin from the mixtures in order to shift the balance to complete conversion with production of ethers.

The scientist of Boreskov Institute of Catalysis used barium hexaaluminate as a heterogeneous catalyst and received good results.

“First the conversion in the process decreases due to ablation of weakly bonded barium from the surface of catalyst. However, the lattice barium that remained showed stability in the second cycle, and we obtained conversion of 75%. If the necessary parameters are selected, then up to 100% conversion of lipids can be reached”, noted the scientist.

According to Vadim Yakovlev, it is necessary to solve several problems to make bioenergetics more efficient.

“We should learn to process the biomass completely with obtaining the products with higher added value. We must optimize logistics of transporting the material to the sites of processing. The industrial chains should be delicately integrated into the infrastructure of oil processing, and the technologies of working with biomass should be at a high technological level”, he summarized.



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