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Optimized process for upgrading bio-oils of aromatic bases

a bio-oil and aromatic base technology, applied in the direction of hydrocarbon oil treatment products, organic chemistry, chemistry apparatus and processes, etc., can solve the problems of difficult storage and use of bio-oil, difficult post-treatment storage and use, poisoning post-treatment catalysts, etc., to maximize naphtha, increase the yield of naphtha fraction, and excellent reactivity

Inactive Publication Date: 2013-12-05
INST FR DU PETROLE
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The patent describes a process for making a gasoline-like product from naphtha. This involves using a catalyst to convert the naphtha into a reformate product that contains aromatic compounds. The process also includes a separation stage where transalkylation stages can be used to increase the yield of BTX (a group of aromatic compounds). Overall, this process allows for the efficient production of a high-quality gasoline product.

Problems solved by technology

The bio-oils of pyrolysis have undesirable properties such as: (1) The corrosiveness due to their high content of water and organic acids; (2) A low specific calorific value because of the high content of oxygen, typically on the order of 40% by weight; (3) Chemical instability, in storage as well as under elevated heat conditions, due to the abundance of reactive oxygenated functional groups such as the carbonyl group, which can bring about polymerization during storage and consequently a separation of phases; (4) A viscosity and a tendency toward the separation of relatively high phases under high shearing conditions, in an injector, for example; (5) Solid coal particles obtained from pyrolysis, which will always be present in non-filtered bio-oils in small amounts such that the bio-oil / coal particles ratio is higher than 10:1 and preferably higher than 50:1.
However, said particles can cause the clogging of stationary internal combustion engines or can poison post-treatment catalysts.
All of these aspects are combined to make handling, shipping, storage and use of the bio-oils difficult and costly, thus making their integration into the systems and the current technologies for production of heat and energy very problematic.
One of the major obstacles to the direct catalytic hydrotreatment of bio-oils resides in their tendency to polymerize when they are subjected to higher temperatures than approximately 100° C., which gives rise to the formation of solids at higher temperatures than approximately 140° C., with consequences such as the clogging of feedstock lines, furnaces and reactors as well as the rapid deactivation of the catalyst, and even the clogging of the inlet of the reactor.
The difficulties encountered find their origin in the rapid thermal polymerization of bio-oil, which leads to the clogging of lines and reaction equipment as well as to rapid deactivation of the catalyst.

Method used

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  • Optimized process for upgrading bio-oils of aromatic bases

Examples

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example 1

Preparation of C1 Hydroreforming Catalysts

[0144]The C1 catalyst is a catalyst of formulation NiCr / C. The precursors of nickel and chromium, in their nitrate form (respectively Ni(NO3)2 and Cr(NO3)3), are provided by Aldrich. The substrate is an activated carbon in the form of cylindrical extrudate provided by the Norit Company (RX3 Extra). This C1 catalyst is obtained by dry impregnation with an aqueous solution that contains the precursors of nickel and chromium. The solution volume is equal to the volume of water uptake of the substrate (i.e., the maximum water volume that can penetrate into its porosity). The concentrations of nickel and chromium precursors in solution are determined in such a way as to obtain the target contents on the final catalyst: 10% by weight of nickel and 5% by weight of chromium. After impregnation of this aqueous solution, the catalyst is allowed to mature at ambient temperature for 4 hours in a water-saturated chamber and then dried in an oven at 70° C...

example 2

Production of a Reformate that Contains More than 70% by Weight of Aromatic Compounds from a Non-Pretreated Bio-Oil

[0145]This example illustrates the production of an oxygen-free reformate that contains more than 70% by weight of BTX aromatic compounds from the treatment of a non-pretreated bio-oil liquid feedstock with the characteristics that are described in Table 1, according to the process of the invention.

[0146]For the first hydroreforming stage, the non-pretreated bio-oil is first introduced, mixed with an organic liquid phase that is obtained from the hydroreforming stage, according to a 1:3 ratio (organic liquid phase:bio-oil) simulating a recycling rate of 0.33, in the autoclave reactor with a hydroreforming catalyst.

[0147]15 g of C1 catalyst prepared according to Example 1 is reduced in a reduction cell at 300° C. for 3 hours in 30 NL / h of hydrogen and then introduced, in a glove bag under inert atmosphere, into a basket that is placed in the autoclave reactor with 75 g o...

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Abstract

A process for preparing aromatic compounds from a liquid biofuel feedstock by introducing the feedstock into a hydroreforming stage in the presence of hydrogen and a hydroreforming catalyst that contains a transition metal of a group 3 to 12 element and an activated carbon, silicon carbide, silica, transition alumina, alumina-silica, zirconium oxide, cerium oxide, titanium oxide, or an aluminate of a transition metal substrate, to obtain a liquid effluent that contains an aqueous phase and an organic phase, a stage for hydrotreatment of the organic phase, a hydrocracking stage, recycling a fraction that boils higher than 160° C. in said hydrocracking stage, a separation into a fraction containing naphtha and a fraction that boils higher than 160° C., a stage for catalytic reforming of the fraction containing naphtha to obtain hydrogen and a reformate that contains aromatic compounds and a stage for separation of the aromatic compounds of the reformate.

Description

FIELD OF THE INVENTION[0001]This invention relates to a process for the production of aromatic compounds starting from liquids obtained from biomass and in particular starting from liquefied biomass obtained from the pyrolysis of biomass, also called bio-oil. In a more specific manner, the invention relates to a process for conversion of bio-oil into BTX-type aromatic compounds comprising a hydroreforming stage, followed by a hydrocracking stage in a fixed bed of rigorous conditions suitable for maximizing the production of light aromatic precursors and a catalytic reforming stage.STATE OF THE ART[0002]The aromatic compounds, in particular the C6-C8 aromatic compounds, i.e., benzene, toluene and xylenes / ethylbenzene (BTX), are major intermediate compounds in petrochemistry for the synthesis of resins, plasticizers and polyester fibers.[0003]The primary BTX production source is the catalytic reforming (or aromatizing according to English terminology) that is used by refiners for impr...

Claims

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Application Information

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Patent Type & Authority Applications(United States)
IPC IPC(8): C10G3/00
CPCC10G3/50C10G3/42C10G69/10C10G2300/1011C10G2400/30Y02P30/20
Inventor QUIGNARD, ALAINTHINON, OLIVIERDULOT, HUGUESHUYGHE, RAPHAEL
Owner INST FR DU PETROLE
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