WO2010012997A2

WO2010012997A2 - Process for production of bio-oil by coprocessing of biomass in a delayed coking unit

Info

Publication number: WO2010012997A2
Application number: PCT/GB2009/001863
Authority: WO
Inventors: Marcio De Figueiredo Portilho; Fernando Antonio Duarte Santiago; Gloria Maria Gomes Soares; Natalie Jorge Goncalves; Danielle Marins Pala; Ana Paula Saraiva De Araujo; Alexander Rangel Bastos; Francisco Carlos Da Costa Barros; Denis Monteiro Da Rocha; Moacir Taparo; Vladimir Albanez Gomes; Fabio Marcelo Souza Brogna; Bruno Milka Souza
Original assignee: Petroleo Brasileiro Sa - Petrobras; Benson, John, Everett
Priority date: 2008-07-31
Filing date: 2009-07-29
Publication date: 2010-02-04
Also published as: AR071766A1; JP2011529523A; WO2010012997A3; CN102099438A; BRPI0803545A2; US20100024283A1

Abstract

A process is described for production of Bio-Oil by delayed coking with modified feedstock, in which the feed of the conventional coke unit envisages, in addition to the usual fresh feed of hydrocarbon (vacuum residue, atmospheric residue etc.), the feeding of a biomass for coprocessing. Said biomass can be selected from the group comprising sugar cane straw, sugar cane bagasse, castor seed cake, coconut shells, rice husks, raw soya, castor seed, canola, oil palm, and cottonseed oils, and oils and fats of animal origin, which can be used separately, or as mixtures thereof in any proportions.

Description

PROCESS FOR PRODUCTION OF BIO-OIL BY COPROCESSING OF

BIOMASS IN A DELAYED COKING UNIT FIELD OF THE INVENTION

The present invention relates to processes of thermal cracking. More specifically the present invention relates to a process for production of Bio- Oil in a delayed coking unit by coprocessing of biomass together with the conventional fresh feed of hydrocarbons . BACKGROUND OF THE INVENTION

The delayed coking process of residual fractions of petroleum has long been used in the oil refining industry. This process makes possible the conversion of heavy petroleum fractions to lighter products of higher added value, for example, liquefied petroleum gas (LPG), naphtha and gas oils from coke.

However, owing to the world oil prices, research is being conducted into renewable energy sources, and the production of fuels from alternative sources, for example, from the transformation of vegetable oils and agricultural waste, is appearing to be more and more promising, owing to the world oil crises.

The present invention presents a process for the production of Bio-Oil in delayed coking units, by the coprocessing of biomass together with a conventional fresh feed of hydrocarbons. RELATED TECHNOLOGY

The delayed coking process, as well as the processing of various types of petroleum-derived feedstocks, are already sufficiently well known.

One of the oldest processes is disclosed in US patent 3,563,884, which describes a process in which coal tar pitch is used as feedstock.

Some variant routes were introduced, based on this invention. US patent 4,213,846 discloses a delayed coking process for the formation of premium coke in which hydrofined gas oil is added to the fresh feed of the unit and fed to the coke drum. Patent US 5,711,870 discloses a delayed coking process in which the fresh feed is mixed with water and, optionally, with a hydrogen donor, such as methane or gas oil derived from the recycle, to optimize the yield of liquid products and lower the yields of coke and gas .

Patent US 4,177,133 describes a delayed coking process for the formation of premium coke in which the fresh feed passes through a stage of preheating and then undergoes flash distillation for removal of noncrystalline substances.

Patents US 4,455,219 and US 4,518,487 present delayed coking processes in which part or all of the heavy hydrocarbon, usually employed as recycle, is replaced with a lighter hydrocarbon, which is combined with the fresh feed of the unit.

Patent US 4,624,775 describes a coking process, preferably a delayed coking, for the production of premium coke in which a mixture of 60 to 90 wt.% of tar obtained from a pyrolysis process and 10 to 40 wt.% of coal tar obtained from a distillation process is employed as feedstock.

Patent US 4,740,293 describes the production of a premium coke, suitable for use in the production of graphite electrodes, from a mixture of tar obtained from a pyrolysis process and hydrofined decanted oil.

Patent US 4,259,78 describes the delayed coking of mixtures of 10% to 30 wt.% of coal and heavy petroleum residues, mixed at temperatures below 50⁰C. Patent US 4,720,338 describes the production of a more uniform premium coke in a delayed coking process by adding an aliphatic fraction of petroleum to the feedstock during the final stages of the cycle, preferably added gradually, in ever increasing amounts. The process described in US patent 5,389,234 relates to the deployment of wet heavy fuel oils in the delayed coking process, which undergo a pretreatment separately, to vaporize and remove water and light hydrocarbons, and are then diluted and heated to a suitable temperature, and are then fed to the top of the coke drums .

Patent EP 0 393 278 describes a process in which the residual oil from the refinery is mixed with an oil for fluidization obtained from delayed coking and this mixture goes to a system for evaporation of the water, comprising several stages of evaporators, and then, after evaporation of the water, the mixture is fed to the top of the coke drum, where it will be subjected to the delayed coking process together with the feedstock of the unit.

At present, with the discovery of heavier and heavier oils, the delayed coking process in the refineries has experienced an increase in its degree of importance, principally due to an increase in the yield of residues from these oils.

Furthermore, modern industrial activities developed by the 14 most industrialized countries generate solid wastes estimated to be of the order of 3.5 billion tonnes per year. The management of these waste products, at all stages: production, transport, storage, processing and distribution, is becoming a matter of considerable global concern. The currently available technologies for the management of solid wastes, including agricultural technologies, aim at minimizing them, the recycling of waste materials, treatment of the latter and disposal in landfill. The efficient application of these technologies could lead to the conversion of the solid wastes into useful products, their reduction, or their elimination, and thermal treatments can significantly reduce the volume and mass of solid wastes and permit recovery of energy, while being able to destroy dangerous and pathogenic components . Technologies for coprocessing of waste materials are being investigated and applied in the management of solid wastes throughout the world, in place of incineration. In the case of pyrolysis, the products obtained are: a gas rich in light hydrocarbons and inorganic compounds, two liquid phases (an aqueous phase and an organic phase) and a solid phase (charcoal). The amount generated of each product depends on the biomass used and on the reaction temperature.

In accordance with the global trend, there is a need to develop processes for the use of renewable raw materials, as well as the recycling of materials that are currently discarded. The present invention fits into this context and offers the possibility of the direct use of biomasses, comprising organic solid wastes and/or vegetable oils, employed separately, or mixed in any proportions, in the delayed coking process. It is becoming clear that the biomasses in question display a considerable potential for being coprocessed with the fresh feeds of hydrocarbons in delayed coking units, using the infrastructure that already exists in oil refineries, or if necessary with some modifications or ajustments to the unit.

The aim of the present invention is to present an innovative solution for the utilization of biomass in the installations already existing in the petroleum industry, through the transformation of vegetable oils or solid wastes of organic origin in conventional delayed coking units into products with higher added value .

The application of this invention makes possible the utilization of various sources of raw material for the production of Bio-Oil, by means of the delayed coking process. SUMMARY OF THE INVENTION

The process for production of a product comprising one or more of fuel gas and LPG (3), light naphtha (4), heavy naphtha (5), light gas oil (6), medium gas oil (7) and heavy gas oil from coke (8), by delayed coking of a modified feedstock, according to the present invention, envisages an innovation that permits the addition of biomasses directly in certain stages of the process, and their coprocessing with the fresh feed of hydrocarbon in a conventional delayed coking unit .

According to the present invention, the feedstock of the conventional delayed coking unit envisages, apart from the fresh feed of hydrocarbon (vacuum residue, atmospheric residue etc.)_/ the feeding of biomass, which can be selected from, but is not limited to, the group comprising raw materials of vegetable origin such as straw from sugar cane, sugar cane bagasse, castor seed cake, coconut shells, rice husks, raw soya, castor seed, canola, oil palm, and cottonseed oils, and raw materials of animal origin such as oils and fats. Biomass of various types and natures can be used in the present invention, fed separately in the industrial units, or mixed in any proportions.

This feed can be effected in the fresh feed of the unit, in the coke drum during the reaction stage or quenching stage (stream of hydrocarbons that lowers the temperature of the effluent), in the inlet line to the furnace, in the outlet line from the furnace or, moreover, in the outlet line from the coke drum. The percentage by volume of said biomass relative to the fresh hydrocarbon feed is in a range of from 0.01% to 80%, preferably in a range of from 0.5% to 30%. BRIEF DESCRIPTION OF THE DRAWINGS

The process for production of a product comprising one or more of fuel gas and LPG (3), light naphtha (4), heavy naphtha (5), light gas oil (6), medium gas oil (7), and heavy gas oil from coke (8) through delayed coking with feedstock modified with biomass, according to the present invention, will be better understood from the detailed description given below, together with the drawings referred to below, which form an integral part of the present specification.

Fig. 1 shows schematically a delayed coking process according to the prior art. Fig. 2 shows schematically a delayed coking process with modified feed, according to a first embodiment of the present invention.

Fig. 3 shows schematically a delayed coking process with modified feed, according to a second embodiment of the present invention.

Fig. 4 shows schematically a delayed coking process with modified feed, according to a third embodiment of the present invention. Fig. 5 shows schematically a delayed coking process with modified feed, according to a fourth embodiment of the present invention.

Fig. 6 shows schematically a delayed coking process with modified feed, according to a fifth embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

The delayed coking process, for production of a product comprising one or more of fuel gas and LPG (3), light naphtha (4), heavy naphtha (5), light gas oil (6), medium gas oil (7) and heavy gas oil from coke (8), characterized in that biomass (14) is coprocessed with modified feed, according to the present invention, will be described on the basis of the diagrams and in its preferred embodiments. Fig. 1 shows schematically a delayed coking process according to the prior art.

A fresh hydrocarbon feed (1) is fed into a fractionating tower (2), from where said product is withdrawn . A bottom product (9) from the fractionating tower (2) is fed into a furnace (10) to initiate thermal cracking. An effluent (11) from the furnace (10) is then sent to a coke drum (12), to complete thermal cracking and coking, producing coke and an effluent (13) from the coke drum (12), comprising light hydrocarbons, which is sent to the fractionating tower (2) .

In a first embodiment of the invention, a process of modification of a feed in a delayed coking unit is represented schematically in Fig. 2, according to which the biomass (14) is added to the fresh feed (1) . As can be seen, the biomass (14) is added to the fresh feed (1), producing a new stream (I¹) which is fed into a fractionating tower (2), from where said product is withdrawn. A percentage by volume of the biomass (14) relative to the fresh feed (1) is used in a range of from _^0.01% to 80%, preferably in a range of from 0.5% to 30%. The bottom product (9) from the fractionating tower (2) is fed into a furnace (10), to initiate thermal cracking. Optionally the fresh feed (1) can be fed to a charging tank (15) or similar apparatus, prior to entering the furnace (10). The effluent (11) from the furnace (10) is then sent to a coke drum (12), to complete thermal cracking and coking, producing coke and an effluent (13) from the coke drum (12), comprising light hydrocarbons. The effluent (13) is then sent to the fractionating tower (2) .

Another possibility for application of the invention is presented in Fig. 3, in which a second embodiment of the invention is represented schematically, in which the biomass is added to the coke drum (12) during the reaction or quenching stage. The details are described below.

A fresh hydrocarbon feed (1) is fed into a fractionating tower (2), from where said product is withdrawn. A bottom product (9) from the fractionating tower (2) is fed into a furnace (10), to initiate thermal cracking. Optionally the fresh feed (1) can be fed to a charging tank (15) or similar apparatus, prior to entering the furnace (10) . An effluent (11) from the furnace (10) is then sent to a coke drum (12) and biomass (14) is added to the coke drum (12), during the reaction or quenching stage, to complete thermal cracking and coking, producing coke and an effluent

(13) from the coke drum (12), comprising light hydrocarbons, which is sent to the fractionating tower (2) . The percentage by volume of the biomass (14) relative to the fresh feed (1) is in a range of from 0.01% to 80%, preferably in a range of from 0.5% to 30%.

In a third embodiment of the invention, presented in Fig. 4, a process of modification of a feed in a delayed coking unit is represented schematically. In this case the biomass (14) is added to the furnace feed line, as described below.

A fresh hydrocarbon feed (1) is fed into a fractionating tower (2), from where said product is withdrawn.

Biomass (14) is added to a bottom product (9) from the fractionating tower (2), producing a new stream (9¹) that is fed into a furnace (10), to initiate thermal cracking. In this case too, the percentage by volume of the biomass (14) relative to the fresh feed (1) is in a range of from 0.01% to 80%, preferably in a range of from 0.5% to 30%. Optionally the fresh feed (1) can be fed to a charging tank (15) or similar apparatus, prior to entering the furnace (10), shown with dashed lines.

An effluent (11) from the furnace (10) is then sent to a coke drum (12), to complete thermal cracking and coking, producing coke and an effluent (13) from the coke drum (12), comprising light hydrocarbons, which is sent to the fractionating tower (2).

Alternatively, in a fourth embodiment of the invention presented in Fig. 5, a process of modification of a feed in a delayed coking unit is represented schematically. In this embodiment the biomass (14) is added to the outlet line from the furnace. The procedure employed is described in detail below.

A fresh hydrocarbon feed (1) is fed into a fractionating tower (2), from where said product is withdrawn. A bottom product (9) from the fractionating tower (2) is fed into a furnace (10), to initiate thermal cracking.

Optionally the fresh feed (1) can be fed to a charging tank (15) or similar apparatus, prior to entering the furnace (10), shown with dashed lines.

Biomass (14) is added to the effluent (11) from the furnace (10), producing a new stream (II¹), which is then sent to a coke drum (12), to complete thermal cracking and coking, producing coke and an effluent

(13) from the coke drum (12), comprising light hydrocarbons, which is sent to the fractionating tower

(2) . The percentage by volume of the biomass (14) relative to the fresh feed (1) is in a range of from 0.01% to 80%, preferably in a range of from 0.5% to

30%.

Moreover, another possibility for application of the invention is presented in Fig. 6, in a fifth embodiment of the invention. In this possibility the biomass (14) is added to the outlet line from the coke drum. The process is carried out as follows. A fresh hydrocarbon feed (1) is fed into a fractionating tower (2) , from where said product is withdrawn.

A bottom product (9) from the fractionating tower (2) is fed into a furnace (10) , to initiate thermal cracking. An effluent (11) from the furnace (10) is then sent to a coke drum (12), to complete thermal cracking and coking, producing coke and an effluent

(13) from the coke drum (12), comprising light hydrocarbons. Biomass (14) is added to the effluent

(13) from the coke drum (12), producing a new stream

(13')_/ which is sent to the fractionating tower (2).

The percentage by volume of the biomass (14) relative to the fresh feed (1) is in a range of from 0.01% to 80%, preferably in a range of from 0.5% to 30%.

EXAMPLES

The present invention will be understood and assessed more easily from the examples presented below. However, these examples are only to be regarded as being representative of the scope of the present invention and do not in any way limit the invention.

EXAMPLE 1 Raw cottonseed oil was processed in a delayed coking unit at the pilot-plant scale. The furnace temperature was maintained at 500⁰C and the pressure at the top of the coke drum was 2 kgf/cm²g.

We obtained mass yields of 58% in the range of diesel oil from coke and 14% in the range of heavy gas oil from coke. The mass yield of coke was 3.5% and that of gas was 18%.

EXAMPLE 2

Refined soya oil was processed in a delayed coking unit at the pilot-plant scale, maintaining the furnace temperature at 500⁰C and the pressure at the top of the coke drum at 2 kgf/cm²g.

We obtained mass yields of 65% in the range of diesel oil from coke and 6% in the range of heavy gas oil from coke. The mass yield of coke was 2.6% and that of gas was 17%.

EXAMPLE 3

A mixture of 90% of vacuum residue derived from the processing of petroleum obtained from the Marlim field (PETROBRAS - Bacia de Campos) and 10% of raw cottonseed oil was processed in a delayed coking unit at the pilot-plant scale. The furnace temperature was

maintained at 500⁰C and the pressure at the top of the coke drum was 2 kgf/cm²g.

We obtained mass yields of 40% in the range of diesel oil from coke and 19% in the range of heavy gas oil from coke. The mass yield of coke was 25% and that of gas was 9%.

As can be seen, although the present invention has been described in its preferred embodiments and with representative examples, the basic concept guiding the present invention of a process for production of Bio- Oil from the coprocessing of biomass together with hydrocarbon feedstock in a delayed coking unit is preserved with respect to its innovative character, in which a person skilled in the art will be able to envisage and put into practice conceivable variations, modifications, changes, adaptations and substitutions that are compatible with the subject matter treated here, though without deviating from the spirit and scope of the present invention, as represented by the appended claims.

Claims

1. Process for production of a product comprising one or more of fuel gas and LPG (3), light naphtha (4), heavy naphtha (5), light gas oil (6), medium gas oil (7) and heavy gas oil from coke (8) characterized in that biomass (14) is added into a delayed coking unit for coprocessing with a fresh hydrocarbon feed, comprising the stages of:

- feeding a fresh hydrocarbon feed (1) into a fractionating tower (2) , from where said product is withdrawn;

- feeding a bottom product (9) from the fractionating tower (2) into a furnace (10) to initiate thermal cracking;

- sending an effluent (11) from the furnace (10) to a coke drum (12) to complete thermal cracking and coking, producing coke and an effluent (13) from the coke drum (12) comprising light hydrocarbons;

- sending the effluent (13) from the coke drum (12) to the fractionating tower (2) .

2. Process for production of a product according to Claim 1, characterized in that said biomass (14) is coprocessed with a fresh hydrocarbon feed (1) in a delayed coking unit.

3. Process for production of a product according to any of Claims 1 or 2, characterized in that said biomass (14) is selected from the group comprising sugar cane straw, sugar cane bagasse, castor seed cake, coconut shells, rice husks, raw soya, castor seed, canola, oil palm, and cottonseed oils, oils and fats of animal origin, which can be used separately, or as mixtures thereof in any proportions.

4. Process for production of a product according to any of the preceding claims characterized in that said biomass (14) is added to said fresh hydrocarbon feed (1) of said delayed coking unit.

5. Process for production of a product according to any of claims 1 to 4, characterized in that said biomass (14) is added to said coke drum (12), during the reaction or quenching stage.

6. Process for production of a product according to any of claims 1 to 5, characterized in that said biomass (14) is added to said bottom product (9) from said fractionating tower (2) .

7. Process for production of a product according to any of claims 1 to 6, characterized in that said biomass (14) is added to said effluent (11) from the furnace (10) .

8. Process for production of a product according to any of claims 1 to 7, characterized in that said biomass (14) is added to said effluent (13) from the coke drum (12) .

9. Process for production of a product comprising one or more of fuel gas and LPG (3), light naphtha (4), heavy naphtha (5), light gas oil (6), medium gas oil (7) and heavy gas oil from coke (8), characterized in that biomass (14) is added into a delayed coking unit for coprocessing with a fresh hydrocarbon feed, comprising the stages of: - feeding a fresh hydrocarbon feed (1) into a charging tank (15) or similar apparatus, prior to entering the furnace (10) for thermal cracking;

- sending the effluent (13) from the coke drum (12) to the fractionating tower (2), from where said product is withdrawn.

10. Process for production of a product according to any one of the preceding claims, characterized in that the percentage by volume of the biomass (14) relative to said fresh hydrocarbon feed (1) is in a range from 0.01% to 80%.

11. Process for production of a product according to claim 10, characterized in that the percentage by volume of the biomass (14) relative to said fresh hydrocarbon feed (1) is in a range of from 0.5% to 30%.