JP2013545841A - Method for producing biofuel and / or biochemical substance - Google Patents

Abstract

(I) contacting the pyrolysis oil with a catalytic cracking catalyst in the presence of a hydrocarbon co-feed at a temperature of 400 ° C. or higher to produce one or more cracked products; (ii) one or more cracked Fractionating the product to produce one or more product fractions; (iii) using one or more product fractions to produce biofuels and / or biochemicals; A process for producing biofuels and / or biochemicals from pyrolysis oil that has not been pretreated or reformed by treatment and / or hydrodeoxygenation.
[Selection figure] None

Description

  The present invention relates to a method for producing biofuels and / or biochemical substances. Furthermore, the present invention provides a method for producing one or more degradation products from pyrolysis oil.

As the supply of crude mineral oil has decreased, it has become increasingly important to use renewable energy sources to produce fuels and chemicals. These fuels and chemicals from renewable energy sources are often referred to as biofuels and biochemicals, respectively. One advantage of using a renewable energy source, is that CO ₂ balance as compared to the feed material conventional mineral source is better.

  Biofuels and / or biochemicals derived from non-edible renewable energy sources such as lignocellulosic materials are preferred because they do not compete with food production. These biofuels and / or biochemicals are also referred to as second generation biofuels and / or biochemicals.

  Lignocellulosic materials such as wood can be pyrolyzed to yield pyrolyzed oil. However, at present it is believed that such cracked oils cannot be converted to biofuels and / or biochemicals in a simple direct or economically interesting manner.

  Ardiyanti et al. In their paper entitled "Process-product studies on pyrolysis oil upgrading by hydrotreatment with Ru / C catalysts" first published at AICHE 2009, spring meeting in April 2009 In existing refining equipment, either hydrotreating or FCC units, because it is not miscible with hydrocarbon feed and shows a high tendency to coke (this leads to blockage of the feed line and reactor) It is not suitable for the purpose of co-supply to As an alternative, a mild hydroprocessing process has been proposed. This paper describes a two-stage hydrotreating of pyrolysis oil obtained by rapid pyrolysis of forest residues. In this product, two phases were formed, a black oil floating on a clear aqueous layer. The oxygen content of this oil was reduced to 12.3% and 11.5% by weight, respectively, by hydrodeoxygenation. In conclusion and view, the FCC experiment with low residue products as co-feeds states that it is in the process of verifying whether the products are actually suitable as feeds for the purification unit.

  MC Samolada et al. Entitled “Production of a bio-gasoline by upgrading biomass flash pyrolysis liquids via hydrogen processing and catalytic cracking” was first published in Fuel, vol. 77, no. 14, p. 1667-1675, 1988. In their paper, the results of fluid catalytic cracking (FCC) of biomass flash pyrolysis liquids show high coking (8-25 wt%) and low quality of the resulting fuel (about 20 wt% phenolic material) Because it is not promising. They further state that efforts to blend biomass flash pyrolysate with petroleum feed prior to catalytic cracking were not successful due to their small miscibility with hydrocarbons. Therefore, in this paper, a two-step process including thermal hydrogenation treatment of biomass flash pyrolysis liquid and subsequent catalytic cracking is proposed. Thermal hydroprocessing is stated to function as a stabilization process for biomass derived feeds to the FCC.

  F. de Miguel Mercader et al., Their Paper entitled “Production of advanced biofuels: Co-processing of upgraded pyrolysis oil in standard refinery units”: Journal of Applied Catalysis B: Environmental, vol. 96, 2010, p. 57-66 states that it is problematic to directly co-process the pyrolysis oil itself in a standard refining unit. A. Oasmaa et al. "Fast pyrolysis of Forestry Residue. 1. Effect of extractives on phase separation of pyrolysis liquids" first published in Energy & Fuels, vol. 17, No. 1, 2003, p. 1-12. In their paper entitled, “The two-phase products are obtained by the rapid pyrolysis process of forest residues. The top phase is different from the bottom phase and is said to contain a substantial amount of hydrocarbon soluble extract and a small amount of water soluble polar compounds. Furthermore, this paper shows that the upper phase has a considerably higher calorific value than the bottom phase.

Ardiyanti et al., AICHE 2009, spring meeting, "Process-product studies on pyrolysis oil upgrading by hydrotreatment with Ru / C catalysts" M.C.Samolada, Fuel, vol.77, no.14, p. 1667-1675, 1988, "Production of a bio-gasoline by upgrading biomass flash pyrolysis liquids via hydrogen processing and catalytic cracking" F. de Miguel Mercader et al., "Production of advanced biofuels: Co-processing of upgraded pyrolysis oil in standard refinery units", Journal of Applied Catalysis B: Environmentsl, vol. 96, 2010, p. 57-66 A. Oasmaa et al., Energy & Fuels, vol. 17, No. 1, 2003, p. 1-12, "Fast pyrolysis of Forestry Residue. 1. Effect of extractives on phase separation of pyrolysis liquids"

  It would be an advance in the art if a pyrolysis oil that had not been pretreated or reformed substantially by hydroprocessing or hydrodeoxygenation could be used for the production of biofuels and / or biochemicals. .

  It would also be an advancement in the art to provide a process that would allow pyrolysis oil that has not been pretreated or reformed substantially by hydrotreating or hydrodeoxygenation to be processed directly in the FCC unit. Will.

Surprisingly, such a process was found here. Therefore, the present invention
(I) contacting the pyrolysis oil with a catalytic cracking catalyst in the presence of a hydrocarbon cofeed at a temperature of 400 ° C. or higher to produce one or more cracked products;
(Ii) separating one or more degradation products to produce one or more product fractions;
(Iii) using one or more product fractions to produce biofuels and / or biochemicals;
A method of producing biofuels and / or biochemicals from pyrolyzed oil that has not been pretreated or reformed by hydroprocessing and / or hydrodeoxygenation, comprising a step.

Step (i) can be performed in a variety of ways, and therefore the present invention also provides several processes for producing one or more degradation products.
In a first aspect, the present invention provides:
(1a) a pyrolysis oil containing an n-hexane extract in the range of 0 wt% or more to 25 wt% or less and not substantially pretreated or reformed by hydrotreatment and / or hydrodeoxygenation Give part;
(1b) contacting the pyrolysis oil or part thereof with a catalytic cracking catalyst in the presence of a hydrocarbon co-feed at a temperature above 400 ° C. to produce one or more cracked products;
A process is provided for producing one or more degradation products comprising steps.

In a second aspect, the present invention provides:
(2a) providing a bottom phase of the pyrolysis oil or part thereof that has not been pretreated or reformed substantially by hydrotreating and / or hydrodeoxygenation;
(2b) contacting the pyrolysis oil or a part of the bottom phase thereof with a catalytic cracking catalyst in the presence of a hydrocarbon co-feed at a temperature of 400 ° C. or higher to produce one or more cracked products;
A process is provided for producing one or more degradation products comprising steps.

In a third aspect, the present invention provides:
(3a) providing a pyrolysis oil or part thereof that has not been pretreated or reformed substantially by hydrotreatment and / or hydrodeoxygenation;
(3b) contacting the pyrolysis oil or part thereof with a catalytic cracking catalyst in the presence of a hydrocarbon cofeed at a temperature of 400 ° C. or higher to produce one or more cracked products;
Wherein the combination of pyrolysis oil or part thereof and hydrocarbon co-feed has a total hydrogen / carbon molar ratio (H / C) of 1: 1 (1/1) or more A process for producing the above decomposition products is provided.

  The process of the present invention advantageously treats pyrolysis oil, which has not been pretreated or reformed substantially by hydrotreating and / or hydrodeoxygenation, directly in a catalytic cracking unit such as an FCC unit. Make it possible to do. The method of the present invention advantageously treats pyrolysis oil in a catalytic cracking unit without the need for such hydroprocessing and / or hydrodeoxygenation to substantially reduce the oxygen content. Enable.

Surprisingly, it has been found that in the process of the present invention, the pyrolysis oil is sufficiently miscible with the hydrocarbon feed, so that co-treatment has been shown to be feasible.
Furthermore, the hydrocarbon cofeed can advantageously provide the hydrogen necessary to convert oxygen in the pyrolysis oil to water.

  Furthermore, as explained below, a synergistic effect is provided by catalytic cracking of pyrolysis oil in the presence of a hydrocarbon co-feed, resulting in separate catalytic cracking of coke formation during the catalytic cracking process. It has been found that it is less than expected based on the total amount of coke formation for each feedstock.

The method is further advantageous in that a large reduction in total acid number (TAN) is obtained by converting the pyrolysis oil feedstock into a catalytic cracking product.
Since no reforming by hydrotreatment is necessary, a simpler and more economical process than the prior art process is obtained. Thus, the method of the present invention advantageously allows a simple, direct and economically interesting route for converting pyrolysis oil into biofuels and / or biochemicals.

In step (i), the pyrolysis oil is contacted with a catalytic cracking catalyst in the presence of a hydrocarbon cofeed at a temperature of 400 ° C. or higher to produce one or more cracked products.
By pyrolyzed oil is herein understood an oil obtained by pyrolysis. Such pyrolysis oil is preferably further understood as an oil obtained by pyrolysis which has not been substantially pretreated or reformed by hydroprocessing and / or hydrodeoxygenation. Advantageously, hydroprocessing and / or hydrodeoxygenation to substantially reduce the oxygen content of the pyrolysis oil can be avoided in the process of the present invention.

Pyrolytic oil is further understood as “total” pyrolytic oil or part thereof. As shown below, in some embodiments, it is preferred to use specific portions of pyrolysis oil.
Preferably, the pyrolysis oil is derived from a renewable energy source, ie preferably the pyrolysis oil is obtained by pyrolysis of a renewable energy source.

  Any renewable energy source known to those skilled in the art to be suitable for providing pyrolysis oil can be used. Preferably, the renewable energy source comprises a cellulosic material, more preferably a lignocellulosic material. Preferably, therefore, the pyrolysis oil is a pyrolysis oil derived from a cellulosic material, more preferably a lignocellulosic material.

  Any suitable cellulose-containing material can be used as a renewable energy source in pyrolysis. Cellulosic materials can be obtained from a variety of plants and plant materials such as agricultural waste, forest residues, sugar residues, and / or mixtures thereof. Examples of suitable cellulose-containing materials include agriculture such as corn stover, soybean stover, corn cobs, rice straw, rice husk, oat husk, corn fiber, wheat, barley, rye, and cereal straw such as oat straw Wastes; turfgrass; forest products such as wood-related materials such as wood and sawdust; waste paper; sugar residues such as bagasse and beet pulp; or mixtures thereof. In a more preferred embodiment, the pyrolysis oil is obtained by pyrolyzing wood and / or wood-related materials such as forest residues, wood chips, and / or sawdust. In other preferred embodiments, the wood and / or wood-related material comprises bark and / or needles. Most preferably, the pyrolysis oil is obtained by pyrolysis of wood and / or wood related materials containing pine wood or forest residues.

  Pyrolysis is understood here as pyrolysis of a preferably renewable energy source at a pyrolysis temperature of 350 ° C. or higher. The concentration of oxygen is preferably lower than that required for complete combustion. More preferably, the pyrolysis is performed in the substantial absence of oxygen that is not generated in situ. A limited amount of oxygen may be generated in situ during the pyrolysis process. Preferably, the pyrolysis is carried out in an atmosphere containing 5% or less oxygen, more preferably 1% or less oxygen, and most preferably 0.1% or less oxygen. In the most preferred embodiment, the pyrolysis is performed in the substantial absence of oxygen.

  The thermal decomposition temperature is preferably 350 ° C. or higher, more preferably 400 ° C. or higher, and most preferably 450 ° C. or higher. The thermal decomposition temperature is further preferably 800 ° C. or lower, more preferably 700 ° C. or lower, and most preferably 650 ° C. or lower.

  The pyrolysis pressure can be varied widely. For practical purposes, pressures in the range of 0.1-5 bar (0.01-0.5 MPa), more preferably in the range of 1-2 bar (0.1-0.2 MPa) are preferred. Atmospheric pressure (about 1 bar or 0.1 MPa) is most preferred.

  In a preferred embodiment, the pyrolysis oil is provided by so-called rapid or flash pyrolysis of a renewable energy source. Such rapid or flash pyrolysis preferably involves rapidly heating the renewable energy source for a very short period of time and then rapidly reducing the temperature of the primary product before chemical equilibrium can occur. Including.

In a preferred embodiment, the pyrolysis oil is
A renewable energy source in the substantial absence of oxygen at a temperature of 350 ° C. or higher, preferably 400 ° C. or higher, preferably 800 ° C. or lower, within 3 seconds, preferably within 2 seconds, more preferably Heat within 1 second, most preferably within 0.5 second;
Hold a renewable energy source at a temperature of 350 ° C. or higher, preferably 400 ° C. or higher, preferably 800 ° C. or lower for 0.03 to 2.0 seconds, preferably 0.03 to 0.60 seconds. Producing one or more pyrolysis products;
Cooling the pyrolysis product to a temperature below 350 ° C. within 1 second, preferably within 0.5 second;
Obtaining pyrolysis oil from pyrolysis products;
Provided by pyrolysis of renewable energy sources, including processes.

  Examples of rapid or flash pyrolysis processes suitable for providing pyrolysis oil are described in A. Oasmaa et al., “Fast pyrolysis of Forestry Residue. 1. Effect of extractives on phase separation of pyrolysis liquids”, Enegry & Fuels, vol. 17, no. 1, 2003, p. 1-12; and A. Oasmaa et al., Fast pyrolysis bio-oils from wood and agricultural residues, Energy & Fuels, 2010, vol. 24, p. 1380-1388; US-487108 U.S. Pat. No. 5,961,786; and U.S. Pat. No. 5,395,455, which are hereby incorporated by reference.

  After pyrolysis of the renewable energy source, a pyrolysis product is obtained which may comprise a gas, a solid (char), one or more oily phases, and optionally an aqueous phase. One or more oily phases are referred to below as pyrolysis oils. The pyrolysis oil can be separated from the pyrolysis product by any method known to those skilled in the art to be suitable for that purpose. This includes conventional methods such as filtration, centrifugation, cyclone separation, extraction, membrane separation, and / or phase separation. The pyrolysis oil may contain, for example, carbohydrates, olefins, paraffins, oxygenates (eg aldehydes and / or carboxylic acids) and / or possibly some residual water. Preferably, the pyrolysis oil contains carbon (on a dry basis) in an amount of 25 wt% or more, more preferably 35 wt% or more, preferably 70 wt% or less, more preferably 60 wt% or less.

The pyrolytic oil further preferably comprises hydrogen (on a dry basis) in an amount of 1% by weight or more, more preferably 5% by weight or more, preferably 15% by weight or less, more preferably 10% by weight or less.
The pyrolysis oil further preferably contains oxygen in an amount of 25% by weight or more, more preferably 35% by weight or more, preferably 70% by weight or less, more preferably 60% by weight or less. Such oxygen content is preferably defined on a dry basis. The dry standard is understood to exclude water.

  The pyrolysis oil may also contain nitrogen and / or sulfur. When nitrogen is present, the pyrolysis oil is preferably 0.001 wt% or more (on a dry basis), more preferably 0.1 wt% or more, preferably 1.5 wt% or less, more preferably Contains nitrogen in an amount up to 0.5% by weight.

  When sulfur is present, the pyrolysis oil is preferably 0.001 wt% or more (on a dry basis), more preferably 0.01 wt% or more, preferably 1 wt% or less, more preferably 0. Contains sulfur in an amount up to 1% by weight.

  When present, the pyrolysis oil is preferably at least 0.1% by weight, more preferably at least 1% by weight, even more preferably at least 5% by weight, preferably at most 55% by weight, more preferably at least 45%. It contains water in an amount of no more than wt%, even more preferably no more than 35 wt%, even more preferably no more than 30 wt%, and most preferably no more than 25 wt%.

Preferably, the pyrolysis oil of the present invention comprises an aldehyde in an amount of 5 wt% or more, more preferably 10 wt% or more, preferably 30 wt% or less, more preferably 20 wt% or less.
Preferably, the pyrolysis oil comprises carboxylic acid in an amount of 5 wt% or more, more preferably 10 wt% or more, preferably 25 wt% or less, more preferably 15 wt% or less.

Preferably, the pyrolysis oil comprises carbohydrate in an amount of 1% by weight or more, more preferably 5% by weight or more, preferably 20% by weight or less, more preferably 10% by weight or less.
Preferably, the pyrolysis oil comprises phenols in an amount of 0.1 wt% or more, more preferably 2 wt% or more, preferably 10 wt% or less, more preferably 5 wt% or less.

Preferably, the pyrolysis oil comprises furfurals in an amount of 0.1 wt% or more, more preferably 1 wt% or more, preferably 10 wt% or less, more preferably 4 wt% or less.
A hydrocarbon co-feed is understood herein as a co-feed comprising one or more hydrocarbon compounds (ie, compounds containing both hydrogen and carbon). The hydrocarbon co-feed is preferably a liquid hydrocarbon co-feed. A liquid hydrocarbon cofeed is understood as a hydrocarbon cofeed that is fed to the catalytic cracking unit in a substantially liquid phase.

  The hydrocarbon co-feed may be any hydrocarbon co-feed known to those skilled in the art to be suitable as a feed for the catalytic cracking unit. Hydrocarbon co-feeds can be, for example, conventional crude (sometimes referred to as petroleum or mineral oil), non-conventional crude (ie, oil produced or harvested using techniques other than traditional oilfield processes). Or from renewable oils (ie oils derived from renewable sources).

Preferably, the hydrocarbon co-feed is preferably derived from conventional crude oil.
In one aspect, the hydrocarbon co-feed is preferably derived from conventional crude oil. Examples of conventional crudes include West Texas Intermediate, Brent, Dubai-Oman, Midway Sunset, or Tapis crudes.

  More preferably, the hydrocarbon co-feed preferably comprises a conventional crude oil or a fraction of renewable oil. Examples of crude oil fractions that can be used as hydrocarbon co-feeds include straight-run (atmospheric pressure) gas oil, flushing distillate, vacuum gas oil (VGO), coker gas oil, and atmospheric residue (“Long Residue”). ) And vacuum residue (“short residue”), and / or mixtures thereof. In one preferred embodiment, the hydrocarbon co-feed comprises long residue and / or vacuum gas oil.

  In one aspect, the hydrocarbon cofeed is initially at a temperature of 100 ° C. or higher, preferably 150 ° C. or higher, measured using distillation according to ASTM-D 2887-06a at a pressure of 1 bar absolute pressure (0.1 MPa). Has a stationary point (IBP). An example of such a hydrocarbon co-feed is vacuum gas oil.

  In a second embodiment, the hydrocarbon co-feed is measured at 220 ° C. or more, more preferably 240 ° C., using distillation at a pressure of 1 bar absolute pressure (0.1 MPa) according to ASTM-D 2887-06a. It has the above initial boiling point (IBP). An example of such a hydrocarbon co-feed is long residue.

  In a further preferred embodiment, 70% or more, preferably 80% or more, more preferably 90% or more, even more preferably 95% or more of the hydrocarbon co-feed is based on ASTM-D 2887-06a. And having a boiling point in the range of 150 ° C. to 600 ° C. as measured using simulated distillation by gas chromatography.

The composition of the hydrocarbon co-feed can vary widely. The hydrocarbon cofeed may include, for example, paraffins, olefins, and aromatics.
In a preferred embodiment, the hydrocarbon cofeed comprises 8 wt% or more elemental hydrogen, more preferably more than 12 wt% elemental hydrogen. A high content of elemental hydrogen, such as a content of 8% by weight or more, allows the hydrocarbon cofeed to act as an inexpensive hydrogen donor in the catalytic cracking process. While not wishing to be bound by any type of theory, it is further believed that the higher weight ratio of hydrocarbon co-feed to pyrolysis allows more reforming of pyrolysis oil by hydrogen transfer reactions. .

  In other embodiments, at least a portion of the hydrocarbon cofeed comprises a paraffinic hydrocarbon cofeed. Examples of such paraffinic hydrocarbon co-feed materials include so-called Fischer-Tropsch derived hydrocarbon streams as described in WO-2007 / 090884 (incorporated herein by reference), or hydroprocessing equipment. Examples include hydrogen-rich feed materials such as products. The Fischer-Tropsch hydrocarbon stream may optionally be obtained by hydroisomerization of hydrocarbons obtained directly in a Fischer-Tropsch hydrocarbon synthesis reaction.

  The hydrocarbon co-feed according to the present invention is preferably at least 1% by weight paraffin, more preferably at least 2% by weight paraffin, most preferably at least 5% by weight paraffin, preferably at most 99% by weight paraffin, more preferably Contains up to 50% by weight paraffin, most preferably up to 20% by weight paraffin, where paraffin is understood to be both normal, cyclo and branched paraffins.

In a particularly preferred embodiment, the hydrocarbon cofeed is
(1) Crude oil such as (normal pressure) light oil, flushing distillate, vacuum light oil (VGO), coker light oil, normal pressure residual oil ("Long Residue") and vacuum residual oil ("Short Residue") A fraction of
(2) Fischer-Tropsch derived hydrocarbon stream and / or hydrotreater product.

In a particularly preferred process, the total feed is
From 0 wt% to 99 wt%, preferably from 0 wt% to 20 wt% Fischer-Tropsch derived hydrocarbon stream and / or hydrotreater product;
-0% by weight to 99% by weight, preferably 0% by weight to 79% by weight, for example, (normal pressure) light oil, flushing distillate, vacuum light oil (VGO), coker light oil, normal pressure residual oil ( "Long Residue"), and crude oil fractions such as vacuum residue ("Short Residue");
1 to 35% by weight or more, preferably 1 to 20% by weight or less of the pyrolyzed oil described herein or a part thereof;
including.

  The weight ratio of pyrolysis oil to hydrocarbon co-feed can vary widely. In order to facilitate co-processing, the hydrocarbon co-feed and pyrolysis oil are preferably 50/50 (5: 5) or more, more preferably 70/30 (7: 3) or more, even more preferably Is supplied to the catalytic cracking unit at a weight ratio of the hydrocarbon co-feed material and pyrolysis oil of 80/20 (8: 2) or more, more preferably 90/10 (9: 1) or more. For practical purposes, the weight ratio of hydrocarbon co-feed to pyrolysis oil is preferably 99.9 / 0.1 (99.9: 0.1) or less. Accordingly, the amount of pyrolysis oil present is preferably 30 wt% or less, more preferably 20 wt% or less, most preferably 10 wt% or less, based on the total weight of the pyrolysis oil and hydrocarbon co-feed. Even more preferably, it is 5% by weight or less. For practical purposes, the amount of pyrolysis oil present is preferably 0.1% by weight or more, based on the total weight of pyrolysis oil and hydrocarbon co-feed.

Preferably step (i) is carried out in a catalytic cracking unit, more preferably in a fluid catalytic cracking (FCC) unit.
The hydrocarbon co-feed and pyrolysis oil can be mixed prior to introduction into the catalytic cracking unit, or they can be added separately to the catalytic cracking unit at the same or different locations.

  In one aspect, the hydrocarbon co-feed and pyrolysis oil are not mixed prior to introduction into the catalytic cracking unit. In this embodiment, the hydrocarbon co-feed and pyrolysis oil can be fed to the catalytic cracking unit simultaneously (ie, in one location) and mixed upon introduction into the catalytic cracking unit; The feed and pyrolysis oil can be added separately (at different locations) to the catalytic cracking unit.

  The catalytic cracking unit can have a plurality of feed material introduction nozzles. Thus, pyrolysis oil and hydrocarbon co-feed can be processed in a catalytic cracking unit by feeding each component through separate feed inlet nozzles, even when both components are not miscible. it can.

  However, it has been found advantageously that the pyrolysis oil can be mixed with a preferably liquid hydrocarbon co-feed. When the pyrolysis oil is mixed with a preferably liquid hydrocarbon co-feed, the pyrolysis oil preferably comprises less than 25% by weight of n-hexane extract; comprises the pyrolysis oil bottom phase; and Pyrolysis oil which gives a mixture having a hydrogen / carbon molar ratio of at least 1/1 when mixed with a liquid hydrocarbon cofeed, preferably. Accordingly, in another preferred embodiment, the hydrocarbon co-feed and pyrolysis oil are mixed prior to introduction into the catalytic cracking unit to provide a feed mixture comprising the hydrocarbon co-feed and pyrolysis oil. In this embodiment, the hydrocarbon co-feed and pyrolysis oil are preferably 10 ° C. or higher, more preferably 20 ° C. or higher, even more preferably 30 ° C. or higher, most preferably 40 ° C. or higher, 80 ° C. or lower, More preferably the mixing is at a temperature in the range between 70 ° C. or less, most preferably 60 ° C. or less. A slightly lower temperature of 10 ° C. or higher may be preferred when the feed mixture includes VGO as a hydrocarbon co-feed, while a slightly higher temperature of 30 ° C. or higher when the feed mixture includes long residue. Temperature may be preferred. Most preferably, a temperature in the range of 10 ° C. to 25 ° C. is preferred when the feed mixture includes VGO as the hydrocarbon co-feed, while 30 ° C. to 50 ° C. when the feed mixture includes long residue. A range of temperatures is preferred.

  The hydrocarbon co-feed and pyrolysis oil can be mixed by any method known to those skilled in the art to be suitable for such purposes. Preferably, the hydrocarbon co-feed and pyrolysis oil are mixed by static mixing, shaking, and / or stirring.

  The feed mixture can optionally be held in a stirred or unstirred feed vessel before being sent to the catalytic cracking unit. It is one of the advantages of the method according to the invention that an unstirred supply vessel can be used, thereby obtaining a simpler operating process and / or saving construction, energy and / or maintenance costs. . Furthermore, experiments show that by using an unstirred feed vessel, the yield can be surprisingly increased and coking can be reduced.

  Preferably, the feed mixture is 10 ° C. or higher, more preferably 20 ° C. or higher, even more preferably 30 ° C. or higher, most preferably 40 ° C. or higher, 80 ° C. or lower, more preferably in such stirred or non-stirred feed vessels. Is maintained at a temperature in the range between 70 ° C. or less, most preferably 60 ° C. or less.

  A slightly lower temperature of 10 ° C. or higher may be preferred when the feed mixture includes VGO as a hydrocarbon co-feed, while a slightly higher temperature of 30 ° C. or higher when the feed mixture includes long residue. High temperatures may be preferred. Most preferably, a temperature in the range of 10 ° C. to 25 ° C. is preferred when the feed mixture includes VGO as the hydrocarbon co-feed, while 30 ° C. to 50 ° C. when the feed mixture includes long residue. A range of temperatures is preferred.

  Preferably, the feed mixture is optionally 10 ° C. or higher, more preferably 20 ° C. or higher, even more preferably 30 ° C. or higher, most preferably 40 ° C. or higher, 80 ° C. or lower, in a stirred or non-stirred feed vessel. More preferably it is held at a temperature in the range between 70 ° C. or less, most preferably 60 ° C. or less, and then injected into the catalytic cracking unit. A slightly lower temperature of 10 ° C. or higher may be preferred when the feed mixture includes VGO as a hydrocarbon co-feed, while a slightly higher temperature of 30 ° C. or higher when the feed mixture includes long residue. High temperatures may be preferred. Most preferably, a temperature in the range of 10 ° C. to 25 ° C. is preferred when the feed mixture includes VGO as the hydrocarbon co-feed, while 30 ° C. to 50 ° C. when the feed mixture includes long residue. A range of temperatures is preferred.

  The feed mixture can then be contacted with a catalytic cracking catalyst in a catalytic cracking unit. The catalytic cracking catalyst may be any catalyst known to those skilled in the art to be suitable for use in the cracking process. Preferably, the catalytic cracking catalyst comprises a zeolite component. Furthermore, the catalytic cracking catalyst can contain an amorphous binder compound and / or a filler. Examples of the amorphous binder component include silica, alumina, titania, zirconia, and magnesium oxide, or combinations of two or more thereof. Examples of the filler include clay (for example, kaolin).

  The zeolite is preferably a large pore zeolite. Examples of the large pore zeolite include zeolites having a porous crystalline aluminosilicate structure having a porous internal cell structure in which the main axis of the pores above is in the range of 0.62 nm to 0.8 nm. The axis of the zeolite is shown in W.M. Meier, D.H. Olson, and Ch. Baerlocher "Atlas of Zeolite Structure Types", 4th revised edition, 1996, Elsevier, ISBN-0-444-10015-6. Examples of such large pore zeolites include FAU or faujasite, preferably synthetic faujasite, such as zeolite Y or X, ultrastable zeolite Y (USY), rare earth zeolite Y (= REY), and rare earth USY (REUSY). ). According to the present invention, USY is preferably used as the large pore zeolite.

  The catalytic cracking catalyst can also include a medium pore zeolite. Medium pore zeolites that can be used in accordance with the present invention include a porous crystalline aluminosilicate structure having a porous internal cell structure with a major axis of pores thereon ranging from 0.45 nm to 0.62 nm. Zeolite. Examples of such medium pore zeolites are of the MFI structure type, for example ZSM-5; MTW type, for example ZSM-12; TON structure type, for example θ-1; FER structure type, for example ferrierite. According to the present invention, ZSM-5 is preferably used as a medium pore zeolite.

  According to other embodiments, blends of large and medium pore zeolites can be used. The ratio of large pore zeolite to medium pore size zeolite in the cracking catalyst is preferably in the range of 99: 1 to 70:30, more preferably in the range of 98: 2 to 85:15.

  The total amount of large pore diameter zeolite and / or medium pore zeolite present in the cracking catalyst is preferably in the range of 5 wt% to 40 wt%, more preferably 10 wt%, based on the total mass of the catalytic cracking catalyst. It is in the range of ˜30% by weight, even more preferably in the range of 10% by weight to 25% by weight.

  The pyrolysis oil is preferably catalytically cracked in the presence of a hydrocarbon co-feed in a reaction zone (the reaction zone is preferably an elongated tubular reactor preferably oriented substantially vertically). Contact with catalyst. The pyrolysis oil, the hydrocarbon co-feed, and the cracking catalyst can each independently flow in the upward or downward direction.

  Preferably, however, the pyrolysis oil and hydrocarbon co-feed flow in parallel flow in the same direction. The catalytic cracking catalyst can be contacted in parallel, counter-flow, or cross-flow form with the flow of such pyrolysis oil and hydrocarbon co-feed. Preferably, the catalytic cracking catalyst is contacted in parallel flow form with a parallel flow of pyrolysis oil and liquid hydrocarbon co-feed.

In a preferred embodiment, step (i) comprises
A catalytic cracking step of cracking the pyrolysis oil and hydrocarbon co-feed in the reaction zone in the presence of a catalytic cracking catalyst to produce one or more cracked products and consumed catalytic cracking catalyst;
A regeneration process for regenerating the spent catalytic cracking catalyst to produce a regenerated catalytic cracking catalyst; and a recycling process for recycling the regenerated catalytic cracking catalyst to the catalytic cracking process;
including.

  The temperature in the catalytic cracking step is preferably in the range of 450 ° C. to 650 ° C., more preferably 480 ° C. to 600 ° C., and most preferably 480 ° C. to 560 ° C.

  The pressure in the catalytic cracking step is preferably in the range of 0.5 bar to 10 bar (0.05 MPa to 1 MPa), more preferably 1.0 bar to 6 bar (0.15 MPa to 0.6 MPa).

  The residence time of the catalytic cracking catalyst in the reaction zone in which the catalytic cracking is performed is preferably in the range of 0.1 seconds to 15 seconds, more preferably 0.5 seconds to 10 seconds.

  Preferably, the mass ratio of catalytic cracking catalyst to the total feed of pyrolysis oil and hydrocarbon co-feed is in the range of 3 to 20. Preferably, the mass ratio of catalytic cracking catalyst to the total feed of pyrolysis oil and hydrocarbon co-feed is at least 3.5. By using a higher mass ratio of catalyst to feed, improved conversion is obtained.

  In a preferred embodiment, the catalytic cracking step further includes a stripping step. Prior to the regeneration step, the spent catalyst can be stripped to recover the product adsorbed on the spent catalyst. These products can be recycled and added to the product stream obtained from the catalytic cracking process.

  In the regeneration step, preferably, the cracking catalyst is combusted in the presence of an oxygen-containing gas in the regenerator, so that the coke deposited on the catalyst as a result of the catalytic cracking reaction is removed by combustion to restore the catalyst activity. Including that. The heat generated in the exothermic regeneration process is preferably used to provide energy for the endothermic catalytic cracking process. The method of the present invention advantageously allows a sufficient amount of coke to be deposited on the catalytic cracking catalyst so that an exothermic regeneration step can be performed without supplying additional heat.

  The regeneration temperature is preferably in the range of 575 ° C to 900 ° C, more preferably 600 ° C to 850 ° C. The pressure in the regenerator is preferably in the range of 0.5 bar to 10 bar (0.05 MPa to 1 MPa), more preferably 1.0 bar to 6 bar (0.1 MPa to 0.6 MPa).

  The regenerated catalytic cracking catalyst can be recycled to the catalytic cracking process. In a preferred embodiment, a side stream of make-up catalyst can be added to the recycle stream of such regenerated catalytic cracking catalyst to compensate for catalyst loss in the reaction zone and regenerator.

As indicated above, step (i) can be performed in various ways.
In the first aspect, part or all of the pyrolyzed oil in step (i) includes pyrolyzed oil containing 25% by weight or less of n-hexane extract or a part thereof.

Accordingly, in the first aspect, step (i) comprises
(1a) providing a pyrolysis oil or a part thereof containing an n-hexane extract in the range of 0 wt% to 25 wt%;
(1b) contacting the pyrolysis oil or part thereof with a catalytic cracking catalyst in the presence of a hydrocarbon co-feed at a temperature above 400 ° C. to produce one or more cracked products;
Including a process of producing one or more degradation products comprising steps.

  An n-hexane extract can be extracted herein from pyrolysis oil into n-hexane (normal hexane) at a temperature of about 20 ° C. and a pressure of about 1 bar absolute pressure (0.1 MPa). Understood as a compound. n-Hexane extracts were published in their paper entitled “Fast Pyrolysis of Forestry Residue. 1. Effect of Extractives on Phase Separation of Pyrolysis Liquids” (vol. 17, No. 1, January / February). , 2003, p. 5 and p. 11) (incorporated herein by reference).

  Examples of such n-hexane extracts include rubber, tannins, flavonoids, lignin monomers (eg guaiacol and catechol derivatives), lignin dimers (stilbenes), resins, waxes, sterols, vitamins, and fungi.

  Preferably, the pyrolysis oil or a part thereof is an n-hexane extract in the range of 0 wt% to 25 wt%, more preferably an n-hexane extract in the range of 0 wt% to 20 wt%. Even more preferably, the n-hexane extract is in the range of 0 wt% to 15 wt%, even more preferably in the range of 0 wt% to 10 wt%, even more preferably 0. An n-hexane extract in the range of from wt% to 6 wt%, most preferably an n-hexane extract in the range of 0 wt% to 3 wt% is included. For practical purposes, a lower limit of 0.01 ppm by weight or more can be considered more preferable within the above range, and a lower limit of 0.1 ppm by weight or more is most preferable within the above range. Can do.

In another particularly preferred embodiment, the pyrolysis oil or part thereof is substantially free of n-hexane extract.
A pyrolysis oil or portion thereof containing up to 25% by weight of n-hexane extract can be obtained by any method known to those skilled in the art to be suitable for this purpose.

  In one aspect, the pyrolysis oil or part thereof comprising up to 25 wt% n-hexane extract is extracted from the pyrolysis oil or part thereof comprising more than 25 wt% n-hexane extract. The product can be obtained by solvent extraction. Suitable solvents for such solvent extraction include n-hexane, but other hexanes, heptanes, pentanes, octanes, nonanes, or decanes are also included. In addition, it may be beneficial to use solvents such as acetone and / or dichloromethane.

  In other embodiments, the pyrolysis oil or a portion thereof is phase separated as described in more detail below, and an n-hexane extract in the range of 0 wt% to 25 wt%, preferably 0 wt%. N-hexane extract in the range of from wt% to 20 wt%, more preferably n-hexane extract in the range of 0 wt% to 15 wt%, even more preferably from 0 wt% to 10 wt%. N-hexane extract in the following range, most preferably a bottom phase pyrolysis oil comprising n-hexane extract in the range of 0 wt% to 6 wt%; and more than 25 wt% n-hexane extract More preferably more than 30% by weight n-hexane extract, more preferably more than 35% by weight n-hexane extract, most preferably more than 40% by weight n-hexane. It includes a distillate, preferably on a phase pyrolysis oil containing 100% by weight of n- hexane extract; can be generated.

  An example of how a pyrolysis oil or part thereof containing up to 25% by weight of n-hexane extract can be obtained is described by A. Oasmaa et al. In Energy & Fuels, an American Chemical Society journal, vol. 17, No. 1, January / February, 2003, p. 1-12 They were entitled "Fast pyrolysis of Forestry Residue. 1. Effect of extractives on phase separation of pyrolysis liquids" Is given in the paper.

In the second aspect, part or all of the pyrolyzed oil in step (i) contains only the bottom phase pyrolyzed oil or part thereof.
Accordingly, in the second aspect, step (i) comprises
(2a) providing a pyrolysis oil or a bottom phase of part thereof;
(2b) contacting the pyrolysis oil or a part of the bottom phase thereof with a catalytic cracking catalyst in the presence of a hydrocarbon co-feed at a temperature of 400 ° C. or higher to produce one or more cracked products;
Including a process of producing one or more degradation products comprising steps.

  In step (2a), a bottom phase of pyrolysis oil is provided. The bottom phase of the pyrolysis oil is understood as the lowest phase that can be obtained when the pyrolysis oil is phase separated. Such phase separation can be performed by the large polarity, solubility, and density differences of the extract and the highly hydrophilic pyrolytic liquid compound. The bottom phase of pyrolysis oil is sometimes referred to as bottom phase pyrolysis oil. The bottom phase pyrolysis oil can be obtained from a pyrolysis oil suitable for phase separation into at least an upper phase and a bottom phase. A pyrolysis oil suitable for phase separation into at least an upper phase and a bottom phase is also understood as a pyrolysis oil that can be separated into at least an upper phase and a bottom phase using a separating agent. Preferably, however, the pyrolysis oil is a pyrolysis oil that can be separated into at least an upper phase and a bottom phase without the need to contact the pyrolysis oil with a separating agent.

Preferably, the pyrolysis oil is phase-separated into at least an upper phase and a bottom phase to produce an upper phase pyrolysis oil and a bottom phase pyrolysis oil. Accordingly, in a preferred embodiment, the present invention provides
(A) providing a pyrolysis oil or part thereof that has not been pretreated or reformed substantially by hydrotreatment and / or hydrodeoxygenation;
(B) phase-separating the pyrolysis oil or a part thereof into at least an upper phase and a bottom phase to produce an upper phase pyrolysis oil and a bottom phase pyrolysis oil;
(C) contacting the bottom phase pyrolysis oil or part thereof with a catalytic cracking catalyst in the presence of a hydrocarbon co-feed at a temperature of 400 ° C. or higher to produce one or more cracked products;
A process is provided for producing one or more degradation products comprising steps.

  Such a process for producing one or more degradation products may then be advantageously used as step (i) in the above-described method for producing biofuels and / or biochemicals from pyrolysis oil. it can. As indicated above, in one embodiment, phase separation can be performed by contacting the pyrolysis oil with a separating agent. A separating agent is understood as a compound that aids in the separation of pyrolytic oil into one or more phases. In a preferred embodiment, such separating agent is an alcohol. Examples of alcohols that can be used as separating agents include ethanol and isopropanol. An example of how isopropanol can be used as a separating agent is their paper entitled “Fast Pyrolysis of Forestry Residue and Pine. 4. Improvement of the Product Quality by Solvent Addition” by Oasmaa et al. and Fuels 2004, vol.18, p.1578-1583). When using an alcohol as the separating agent, the alcohol is preferably 0.25 wt% or more, more preferably 0.5 wt% or more, even more preferably based on the total combination of alcohol and pyrolysis oil. 1 wt% or more, most preferably 2 wt% or more; preferably 10 wt% or less, more preferably 7 wt% or less, most preferably 5 wt% or less, based on the total combination of alcohol and pyrolysis oil Be present in an amount of.

  In other embodiments, phase separation can be performed by reducing (cooling) the temperature of the pyrolysis oil after production. When the phase separation is carried out by cooling, the pyrolysis oil is preferably cooled to a temperature of 15 ° C or higher, more preferably 25 ° C or higher, preferably 50 ° C or lower, more preferably 45 ° C or lower. Examples of how cooling can be used to separate multiple phases are those entitled “Fast Pyrolysis of Forestry Residue. 1. Effect of Extractives on Phase Separation of Pyrolysis Liquids” by Oasmaa et al. (Energy & Fuels, 2003, vol. 17, p. 1-12).

  The bottom phase pyrolysis oil can then be separated from the pyrolysis upper phase by any method known to those skilled in the art to be suitable for this purpose. Examples of phase separation methods include sedimentation, decantation, centrifugation, cyclone separation, extraction, and membrane technology.

  In the process of the present invention, the bottom phase pyrolysis oil that is contacted with the catalytic cracking catalyst in the presence of a hydrocarbon cofeed at a temperature of 400 ° C. or higher to produce one or more cracked products is a small amount of bottom phase. It may be contaminated with other phases other than pyrolysis oil. These small amounts of other phases may be dispersed or dissolved in, for example, bottom phase pyrolysis oil. Preferably, the total amount of pyrolysis oil to be contacted with the catalytic cracking catalyst in the method of the present invention is 90% by weight or more, more preferably 95% by weight or more, based on the total weight of the pyrolysis oil to be contacted with the catalytic cracking catalyst. More preferably 99% by weight or more, still more preferably 99.9% by weight or more, most preferably 99.99% by weight or more of the bottom phase pyrolyzed oil.

  Preferably, the amount of any other phase pyrolysis oil (ie not bottom phase pyrolysis oil, which is also referred to as non-bottom phase pyrolysis oil) is the total weight of pyrolysis oil contacted with the catalytic cracking catalyst. Is 10% by weight or less, more preferably 5% by weight or less, still more preferably 1% by weight or less, still more preferably 0.1% by weight or less, and most preferably 0.01% by weight or less. Most preferably, the pyrolysis oil that is contacted with the catalytic cracking catalyst in the process of the present invention consists essentially of bottom phase pyrolysis oil. That is, most preferably, the catalytic cracking is conducted in the substantial absence of non-bottom phase pyrolysis oil.

An example of non-bottom phase pyrolysis oil is top phase pyrolysis oil.
In a preferred embodiment, the bottom phase pyrolysis oil is an n-hexane extract in the range of 0 wt% to 25 wt%, more preferably an n-hexane extract in the range of 0 wt% to 20 wt%. Even more preferably, the n-hexane extract is in the range of 0 wt% to 15 wt%, even more preferably in the range of 0 wt% to 10 wt%, even more preferably 0. An n-hexane extract in the range of from wt% to 6 wt%, most preferably an n-hexane extract in the range of 0 wt% to 3 wt% is included.

  Further, the bottom phase pyrolysis oil can be water (preferably in the range of 20-35% by weight), carboxylic acid (preferably in the range of 5-15% by weight), alcohol (preferably in the range of 0-5% by weight), carbohydrates. (Preferably in the range of 25-40% by weight) and / or lignin compounds (preferably in the range of 5-30% by weight).

In a third embodiment, part or all of the pyrolysis oil in step (i) preferably gives a mixture having a hydrogen / carbon molar ratio of at least 1/1 when mixed with a liquid hydrocarbon co-feed. Pyrolysis oil or part thereof. Accordingly, in the third aspect, step (i) comprises:
(3a) providing pyrolysis oil or part thereof;
(3b) contacting the pyrolysis oil or part thereof with a catalytic cracking catalyst in the presence of a hydrocarbon cofeed at a temperature of 400 ° C. or higher to produce one or more cracked products;
Wherein the mixture of pyrolysis oil or part thereof and hydrocarbon co-feed has a total hydrogen / carbon molar ratio (H / C) of 1: 1 (1/1) or higher (H / C) A process for producing the above decomposition products.

  The mixture of pyrolysis oil or part thereof and preferably a liquid hydrocarbon co-feed is preferably 1.1: 1 (1.1 / 1) or more, more preferably 1.2: 1 (1.2 / 1) or more, most preferably 1.3: 1 (1.3 / 1) or more of the total hydrogen / carbon molar ratio (H / C).

In a preferred embodiment, an effective hydrogen / carbon molar ratio (H / C _eff ) is used. The effective hydrogen / carbon molar ratio (H / C _eff ) means the total number of moles of oxygen present in the oil on a dry basis, assuming no nitrogen or sulfur is present, and water production with the originally present hydrogen. _Is understood as the hydrogen / carbon molar ratio (H / C _eff = (H−2 · O) / C) after theoretical removal.

Preferably, the mixture of pyrolysis oil or part thereof and preferably liquid hydrocarbon co-feed is 1: 1 or more, more preferably 1.1: 1 (1.1 / 1) or more, even more preferably It has a hydrogen / carbon total effective molar ratio (H / C _eff ) of 1.2: 1 (1.2 / 1) or higher, most preferably 1.3: 1 (1.3 / 1) or higher.

In one aspect, the desired hydrogen / carbon molar ratio (H / C) or the desired effective molar ratio of hydrogen / carbon (H / C _eff ) can be obtained by using a specific hydrocarbon co-feed. it can. Examples of suitable hydrocarbon co-feed materials are listed above. The most preferred hydrocarbon co-feed in this regard is long residue.

In other embodiments, the desired molar ratio of hydrogen / carbon (H / C) or the desired effective molar ratio of hydrogen / carbon (H / C _eff ) is a specific weight ratio of pyrolysis oil and hydrocarbon co-feed. It can be obtained by using a material. Examples of suitable weight ratios of pyrolysis oil and hydrocarbon co-feed are listed above. The most preferred weight ratio of hydrocarbon co-feed to pyrolysis oil in this respect is in the range of 7: 3 to 9: 1.

  In step (i) of the method of the present invention, one or more kinds of decomposition products are produced. These one or more degradation products can be further processed in any manner known to those skilled in the art to be suitable for further processing of these products. Such further treatment includes, for example, fractionation and / or hydrotreatment (eg, hydrodesulfurization, hydrodenitrogenation, hydrodeoxygenation, and / or hydroisomerization) of one or more decomposition products. Can be mentioned. Preferably, the one or more degradation products are fractionated into one or more product fractions. Examples of such product fractions include dry gases (such as carbon monoxide, carbon dioxide, methane, ethane, ethene, hydrogen sulfide, and hydrogen), LPG (such as propane and butanes with small amounts of propene and butenes), Gasoline (boiling point in the range of C5 to 221 ° C), light circulating oil (LCO; boiling point in the range of 221 ° C to 370 ° C), heavy circulating oil (HCO; boiling point in the range of 370 ° C to 425 ° C), and / or Slurry oil (boiling point at a temperature higher than 425 ° C.).

  In a preferred embodiment, the one or more cracked products comprise gasoline and LCO in the range of 20% to 90% by weight, more preferably gasoline and LCO in the range of 30% to 80% by weight. .

  In a preferred embodiment, biofuels and / or biochemicals can be produced using product fractions obtained after fractionating one or more degradation products. For example, one or more degradation products can be blended with one or more other ingredients to produce a biofuel and / or biochemical.

Biofuels and biochemicals, respectively, are understood herein as fuels and chemicals respectively derived from at least partially renewable energy sources.
Examples of one or more other ingredients that can be blended with one or more product fractions include antioxidants, corrosion inhibitors, ashless detergents, defogging agents, dyes, lubricity Examples include improvers and / or mineral fuel components.

  The invention further includes a combination of aspects described in the above description.

The invention is illustrated by the following non-limiting examples.
Example 1: Mixing bottom phase pyrolysis oil and hydrocarbon co-feed derived from forest residues:
Pyrolysis oil derived from forest residues was obtained from VTT. Pyrolysis of forest residues is described by Oasmaa et al. In their paper "Fast pyrolysis of Forestry Residue. 1. Effect of Extractives on Phase Separation of Pyrolysis Liquids", Energy & Fuels, 2003, 17, p. 1-12. This was done using a process development unit (PDU) with a capacity of 20 kg / hr. Bottom phase pyrolysis oil and top phase pyrolysis oil were obtained as described in this paper.

next,
Upper phase pyrolysis oil from 20% by weight forest residue and 80% by weight vacuum gas oil (VGO);
A bottom phase pyrolysis oil from 20% by weight of forest residues and a heavy feed mixture of 80% by weight;
A mixture of was prepared.

  In order to determine miscibility, the following visual test was performed. Each mixture was heated to about 65 ° C. in a glass bottle and stirred vigorously. Thereafter, the glass bottle was allowed to stand at 65 ° C. for 30 minutes. The glass bottle was then turned upside down to see if two separate layers of liquid were visible. When the glass bottle is placed upside down at 65 ° C. for 30 minutes and then turned upside down, the pyrolysis oil fraction is immiscible by the dark brown sticky substance at the bottom of the glass bottle.

Details regarding the composition of the top phase pyrolysis oil, bottom phase pyrolysis oil, VGO, and heavy feed mixture can be found in Table 1.
Further details regarding the composition of the VGO and heavy feed mixtures are given in Tables 2 and 3, respectively. Table 4 shows the visual test results of the miscibility of top phase pyrolysis oil and VGO from 20% forest residue and bottom phase pyrolysis oil and heavy feed mixture from 20% forest residue.

Example 2: Catalytic cracking of a mixture of upper phase pyrolysis oil and VGO from forest residues in an unstirred feed vessel:
A mixture of upper phase pyrolysis oil and 20 wt% vacuum gas oil (VGO) from 20 wt% forest residue prepared in Example 1 was transferred as a feed mixture to the feed vessel of the MAT-5000 fluid catalytic cracking unit. During the transfer, the supply container was maintained at 60 ° C. The feed container was not agitated. The first test run was started immediately after the feed mixture was transferred into the feed vessel.

The first test run included seven experiments using seven catalyst to oil ratios, ie catalyst / oil ratios of 3, 4, 5, 6, 6.5, 7, and 8.
Each experiment was performed as follows.

  10 g of FCC equilibrium catalyst containing ultrastable zeolite Y was constantly fluidized with nitrogen. An exact known amount of feed was injected and then nitrogen was flushed through the tube into the fluidized catalyst bed for a 1 minute run time. The fluidized catalyst bed was maintained at 500 ° C. The liquid FCC product was collected in a glass receiver at -18 to -19 ° C.

The FCC catalyst was then stripped with nitrogen for 11 minutes. The gas produced during such stripping was weighed and analyzed online using a gas chromatograph (GC). The FCC catalyst was then regenerated in situ at 650 ° C. for 40 minutes in the presence of air. During such regeneration, coke is converted to CO _2, which was quantified by online infrared measurement. After regeneration, the reactor was cooled to the decomposition temperature and a new injection was started. One cycle including all catalyst / oil ratios took about 16 hours.

  The results of Example 2 are reflected in Table 5 below.

  As shown in Table 5, the production amounts of gasoline and coke in the first and second operations show a large difference. The poor reproducibility for the first and second test runs in Example 2 indicates poor miscibility of the upper phase pyrolysis oil and VGO. Thus, the process in Example 5 may be less robust when scaled up to commercial scale.

As further shown in Table 5, a significant amount of gasoline is produced, which can be used for the production of biofuel.
Example 3: Catalytic cracking of a mixture of bottom phase pyrolysis oil and heavy feed mixture from forest residue in an unstirred feed vessel:
A mixture of bottom phase pyrolysis oil from 20 wt% forest residue and 80 wt% heavy feed mixture prepared in Example 1 was transferred as feed mixture to the feed vessel of the MAT-5000 fluid catalytic cracking unit. For Example 3, the same process as described for Example 2 was performed except that the fluidized catalyst bed was maintained at 520 ° C. rather than 500 ° C. during catalytic cracking.

  The results of Example 3 are reflected in Table 6 below.

  The good reproducibility for the first and second test runs in Example 3 indicates good miscibility of the bottom phase pyrolysis oil and the heavy feed mixture. Thus, the process in Example 5 is robust enough to allow it to scale to commercial scale. Furthermore, the coke yield is considerably lower than the coke yield obtained in Example 2 using the upper phase of pyrolysis oil and using VGO as co-feed.

  Furthermore, as shown in Table 7, elemental analysis of the total liquid product shows a significant decrease in the amount of residual oxygen. Thus, while not wishing to be bound by any kind of theory, it is possible to increase the total acid number directly by co-processing the pyrolysis oil bottom phase and heavy feed mixture in the FCC unit in accordance with the process of the present invention. A decrease is also expected to be led. Thus, the method of the present invention can also advantageously allow further downstream processing of pyrolysis oil that has been catalytically cracked in a refinery.

As further shown in Table 6, a substantial amount of gasoline is produced, which can be used for the production of biofuel.
Example 4: Mixing of bottom phase pyrolysis oil derived from pine and liquid hydrocarbon cofeed:
Pyrolysis oil derived from pine was obtained from VTT. The pyrolysis of pine is described by Oasmaa et al. In their paper "Fast pyrolysis of Forestry Residue. 1. Effect of Extractives on Phase Separation of Pyrolysis liquids", Energy & Fuels, 2003, 17, p. 1-12. It was done like that. A top phase pyrolysis oil from pine and a bottom phase pyrolysis oil from pine were obtained as described in the same paper. next,
Bottom phase pyrolysis oil from 20% by weight pine and 80% by weight heavy feed mixture;
A mixture of was prepared.

  Details about the composition of the bottom phase pyrolysis oil and heavy feed mixture from pine can be found in Table 8.

Example 5: Catalytic cracking of a mixture of pine-derived bottom phase pyrolysis oil and heavy feed mixture in unstirred and stirred feed vessels:
For Example 5, the same process as described for Example 3 except that the mixture prepared in Example 4 was used, the feed vessel was maintained at 50 ° C., and the process was conducted in stirred and non-stirred feed vessels. Went. The supply container was agitated by a tower top stirrer having four blades immersed in the supply container. The results are summarized in Table 9.

  As can be seen in Table 9, consistent and reproducible results can be obtained for the entire time of an operating cycle (approximately 16 hours) in both unstirred and stirred feed vessels. This shows that the method of the invention advantageously makes it possible to carry out the process without stirring the feed vessel. As a result, this process can be scaled more easily.

As further shown in Table 9, a significant amount of gasoline is produced, which can be used for the production of biofuel.
Example 6: Catalytic cracking of a mixture of bottom phase pyrolysis oil and heavy feed mixture on a pilot scale:
following:
(1) a feed comprising 100% by weight conventional crude fraction; and (2) 9.5% by weight bottom phase pyrolysis oil, 1% by weight surfactant, and 89.5% by weight conventional. Feedstock consisting of a blend of type crude oil fractions;
Two experiments were carried out using.

  Each of the above feeds of each of the above blends was heated to 82 ° C. and transferred as a feed mixture to the feed vessel of a pilot scale fluid catalytic cracking unit. The pilot scale fluid catalytic cracking unit consisted of six sections including feed feed system, catalyst loading and transfer system, riser reactor, stripper, product separation and recovery system, and regenerator. The riser reactor was an adiabatic riser having an inner diameter of 11 mm and a length of about 3.2 m. The riser reactor outlet was in fluid communication with a stripper that was operated to provide substantially 100% stripping efficiency at the same temperature as the riser reactor outlet stream. The regenerator was a multistage continuous regenerator used to regenerate spent catalyst. The spent catalyst was supplied to the regenerator at a controlled rate, and the regenerated catalyst was recovered in the container. The catalytic cracking catalyst contained ultrastable zeolite Y.

  Material balance was obtained at 30 minute intervals between each experimental run. The composite gas sample was analyzed overnight by using an on-line gas chromatograph, and the liquid product sample was collected and analyzed. Coke by measuring the catalyst flow and measuring the Δ coke on the catalyst determined by measuring the consumption taken and the coke on the regenerated catalyst sample for each run when the unit is operating in steady state. The yield was measured.

  The feed characteristics are given in Table 10 below. The results are summarized in Table 11.

Comparative Example 7:
The experiment was conducted as described above with respect to Example 6 except that the feedstock contained 100 wt% bottom phase pyrolysis oil. Within 10 minutes from the start of the feed pump, the experiment failed because the supply line to the riser and the feed nozzle were quickly blocked due to coke formation.

Claims (12)

(I) contacting the pyrolysis oil with a catalytic cracking catalyst in the presence of a hydrocarbon cofeed at a temperature of 400 ° C. or higher to produce one or more cracked products;
(Ii) separating one or more degradation products to produce one or more product fractions;
(Iii) using one or more product fractions to produce biofuels and / or biochemicals;
A process for producing biofuels and / or biochemicals from pyrolysis oil that has not been pretreated or reformed substantially by hydrotreating and / or hydrodeoxygenation, comprising a step. Step (i)
(1a) providing a pyrolysis oil or a part thereof containing an n-hexane extract in the range of 0 wt% to 25 wt%;
(1b) contacting the pyrolysis oil or part thereof with a catalytic cracking catalyst in the presence of a hydrocarbon co-feed at a temperature above 400 ° C. to produce one or more cracked products;
The method of claim 1, comprising a process of producing one or more degradation products comprising steps. Step (i)
(2a) providing a pyrolysis oil or a bottom phase of part thereof;
(2b) contacting the pyrolysis oil or a part of the bottom phase thereof with a catalytic cracking catalyst in the presence of a hydrocarbon co-feed at a temperature of 400 ° C. or higher to produce one or more cracked products;
3. A method according to claim 1 or 2, comprising a process for producing one or more degradation products comprising steps. Step (i)
(3a) providing pyrolysis oil or part thereof;
(3b) contacting the pyrolysis oil or part thereof with a catalytic cracking catalyst in the presence of a hydrocarbon cofeed at a temperature of 400 ° C. or higher to produce one or more cracked products;
Including a process to produce one or more cracked products comprising a step, wherein the combination of pyrolysis oil or part thereof and hydrocarbon co-feed is 1: 1 (1/1) or more hydrogen / carbon 4. A process according to claim 1, 2 or 3 having a total molar ratio (H / C).   The method of any one of claims 1-4, wherein the pyrolytic oil is derived from a lignocellulosic material.   6. A method according to claim 5, wherein the lignocellulosic material is selected from the group consisting of wood, wood-related materials, and / or mixtures thereof.   The process according to any one of claims 1 to 6, wherein the hydrocarbon co-feed is derived from conventional crude oil.   The hydrocarbon co-feed material is selected from the group consisting of straight-run gas oil, flushing distillate, vacuum gas oil, coker gas oil, atmospheric residue, and vacuum residue. The method described.   9. A method according to any one of the preceding claims, wherein the hydrocarbon co-feed comprises 8 wt% or more elemental hydrogen.   10. The hydrocarbon co-feed has any initial boiling point (IBP) of 220 ° C. or higher as measured using distillation based on ASTM-D2887-06a at a pressure of 0.1 MPa. The method described in 1.   Before introducing into the catalytic cracking unit, the hydrocarbon co-feed and the pyrolysis oil or bottom phase of pyrolysis oil are mixed to provide a feed comprising the hydrocarbon co-feed and pyrolysis oil or pyrolysis oil bottom phase. 11. A method according to any one of the preceding claims, wherein a mixture is provided.   12. The method of claim 11, wherein the hydrocarbon co-feed is mixed with the pyrolysis oil or pyrolysis oil bottom phase by agitation.