CN102099438A - Process for production of bio-oil by coprocessing of biomass in a delayed coking unit - Google Patents

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

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Publication number
CN102099438A
CN102099438A CN2009801282619A CN200980128261A CN102099438A CN 102099438 A CN102099438 A CN 102099438A CN 2009801282619 A CN2009801282619 A CN 2009801282619A CN 200980128261 A CN200980128261 A CN 200980128261A CN 102099438 A CN102099438 A CN 102099438A
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China
Prior art keywords
biomass
product
coke
effluent
oil
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Pending
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CN2009801282619A
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Chinese (zh)
Inventor
M·D·F·伯提尔豪
F·A·D·桑提亚高
G·M·G·索尔瑞斯
N·J·冈卡尔韦斯
D·M·帕拉
A·P·S·德阿劳尤
A·R·巴斯图斯
F·C·D·C·巴洛斯
D·M·达罗扎
M·塔帕罗
V·A·高梅斯
F·M·S·布罗格纳
B·M·索扎
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Brazil Petroleum Co
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Brazil Petroleum Co
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Publication of CN102099438A publication Critical patent/CN102099438A/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/04—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
    • C10B57/12—Applying additives during coking
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/40—Thermal non-catalytic treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G51/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only
    • C10G51/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only
    • C10G51/023—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more cracking processes only plural serial stages only only thermal cracking steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/005—Coking (in order to produce liquid products mainly)
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1018—Biomass of animal origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/26—Fuel gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/28—Propane and butane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Processing Of Solid Wastes (AREA)
  • Coke Industry (AREA)

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

The method for preparing bio oil by the co-processing of biomass in delayed coking unit
Technical field
The present invention relates to the method for thermally splitting.More particularly, the present invention relates to be used for prepare the method for bio oil at delayed coking unit with the co-processing of traditional fresh hydrocarbon charging by biomass.
Background technology
The delayed coking method of the residual fraction of oil has been used for petroleum refining industry for a long time.This method can be converted into heavier petroleum fraction light product, for example liquefied petroleum gas (LPG) (LPG), petroleum naphtha and the gas oil of higher increased value by coke.
Yet because the research of renewable energy source has been carried out in the influence of world petroleum price, because world oil crisis, as if by the alternative energy, for example preparing fuel by the transformation of vegetables oil and agricultural waste more and more has prospect.
The present invention has presented and has been used for preparing the method for bio oil by biomass at delayed coking unit with the co-processing of conventional fresh hydrocarbon charging.
Correlation technique
Delayed coking method and the various processing that is derived from the raw material of oil have been fully known.
One of the oldest method is disclosed in United States Patent (USP) 3,563, and in 884, it has been described wherein with the method for coal-tar pitch as raw material.
Some different approach have been introduced based on this invention.United States Patent (USP) 4,213,846 disclose the delayed coking method that is used to generate senior coke, wherein hydrogenation purified gas oil are added in the fresh feed of this device and supply with coke drum.
United States Patent (USP) 5,711,870 disclose delayed coking method, wherein fresh feed and water and optional hydrogen donor (for example methane or from round-robin gas oil) are mixed with the productive rate of optimization product liquid and reduce coke and the productive rate of gas.
United States Patent (USP) 4,177,133 have described the delayed coking method that is used to prepare senior coke, wherein fresh feed are also passed through flash distillation to remove amorphous material then by the pre-warmed stage.
United States Patent (USP) 4,455,219 and 4,518,487 have presented delayed coking method, wherein use the some or all heavy hydrocarbons that replace being used as usually recycle with the fresh feed bonded of this device than lighter hydrocarbons.
United States Patent (USP) 4,624,775 have described the coking method that is used to prepare senior coke, preferred delayed coking, the mixture of the coal tar that is obtained by distillating method that wherein uses the tar that is obtained by method for pyrolysis of 60-90wt% and 10-40wt% is as raw material.
United States Patent (USP) 4,740,293 have described and utilize the tar that obtained by method for pyrolysis and the mixture preparation of hydrogenation purified clarified oil to be applicable to the senior coke of producing Graphite Electrodes.
United States Patent (USP) 4,259,78 have described the delayed coking at the mixture that is lower than 50 ℃ temperature blended 10%-30wt.% coal and heavy crude residual oil.
United States Patent (USP) 4,720,338 described by in round-robin final stage process with ever-increasing amount with the aliphatics cut of oil add to (preferably add gradually) in the raw material and in delayed coking method the method for the more uniform senior coke of preparation.
United States Patent (USP) 5,389, the method for describing in 234 relates to utilizes weight in wet base matter oil fuel in delayed coking method, its individually through pre-treatment with evaporation and remove and anhydrate and light hydrocarbon, dilute then and be heated to suitable temperature, supply with the top of coke drum then.
European patent 0 393 278 has been described a kind of method, wherein will mix with the fluidizing oil that is used for that obtains by the delay cracking from the irreducible oil of refinery, and this mixture sent into the system's (comprising several evaporator stages) that is used for vaporize water, and then after evaporating off water, this mixture is supplied with the top of this coke drum, and it will pass through this delayed coking process with the raw material of this device herein.
At present, along with the discovery of more and more heavier oil, the delayed coking method in the refinery is through the raising of its significance level, mainly is because the productive rate of the residual oil that obtains from these oil is improved.
Estimate to be about 3,500,000,000 tons/year solid waste by movable generation of the modern industry of 14 country that industrialization degree is the highest exploitations in addition.These refuse products become appreciable global concern incident in the management of all stages (preparation, transportation, storage, processing and distribution).Known technology (the comprising agrotechnique) target that is used to manage solid waste is to make it to minimize, the refuse material is circulated, handles the latter and landfill disposal at present.Effective use of these technology can cause solid waste to be converted into useful product, and its minimizing or its are removed, and thermal treatment can significantly reduce the volume and the quality of solid waste and energy recovery is provided, and can destroy deleterious and morbific component simultaneously.
The whole world to Management of Solid Waste in research and the technology generation of having used the co-processing that is used for the refuse material for burning.In the pyrolytic situation, resulting product is: the gas, two liquid phases (water and organic phase) and the solid phase (charcoal) that are rich in light hydrocarbon and mineral compound.The generation of each product depends on used biomass and temperature of reaction.
According to worldwide trend, there is the demand of developing the material cyclic utilization method of using renewable raw materials and will abandoning at present.
The present invention adapts to this background and the possibility of directly using separately or mixing with arbitrary proportion the biomass of using that comprise organic solid waste and/or vegetables oil in delayed coking method is provided.
Obviously the visual target biomass have shown in the use petroleum refinery existing basic structure or if necessary device have been carried out some improvement or adjusting, in delayed coking unit with the important potentiality of fresh hydrocarbon charging co-processing.
The objective of the invention is to present the product that in traditional delayed coking unit, changes higher increased value by the solid waste of vegetables oil or organic origin into, in petroleum industry, use the innovation scheme of biomass in the existing device.
Applicant of the present invention can use the raw material in various sources to prepare bio oil by means of postponing switching method.
Summary of the invention
According to the present invention, be used for delayed coking preparation by modified feedstock and comprise fuel gas and LPG (3), light naphtha (4), heavy naphtha (5), lightweight gas oil (6), matter gas oil (7) and biomass directly can be added to from one or more the method imagination of product in the heavy gas oil (8) of coke in some stage of this method and and postpone the innovation of co-processing in the switch in tradition with the fresh hydrocarbon charging with it.
According to the present invention, the raw material imagination of this tradition delayed coking unit is also supplied with biomass except fresh hydrocarbon charging (vacuum resid, long residuum etc.), it can be selected from but be not limited to and comprise following group: the raw material of plant origin, for example sugarcane bar, bagasse, castorseed cake, Exocarpium cocois (Cocos nucifera L), rice husk, soy material, castor seeds, Semen Brassicae campestris, coconut oil and Oleum Gossypii semen, with the raw material of animal-origin, for example oil ﹠ fat.The biomass energy of all kinds and character is enough among the present invention, mixes in the supply full scale plant separately or with arbitrary proportion.
This charging can the coke drum in the fresh feed of this device, in step of reaction or chilling phase process in (reducing the hydrocarbon stream of the temperature of effluent), the source line, realize in the outlet line at stove or in the outlet line of this external coke drum at stove.Described biomass with respect to the volume percent of fresh hydrocarbon charging in the scope of 0.01%-80%, preferably in the scope of 0.5%-30%.
Description of drawings
From with detailed description given below that the accompanying drawing of the integral part of this specification sheets of formation described below combines, be used for comprising fuel gas and LPG (3), light naphtha (4), heavy naphtha (5), lightweight gas oil (6), matter gas oil (7) and will being better understood according to the present invention from one or more the method for product in the heavy gas oil (8) of coke by delayed coking preparation with biomass modified raw material.
Fig. 1 has schematically shown the delayed coking method according to prior art.
Fig. 2 has schematically shown the delayed coking method according to the modified feedstock of first embodiment of the present invention.
Fig. 3 has schematically shown the delayed coking method according to the modified feedstock of second embodiment of the present invention.
Fig. 4 has schematically shown the delayed coking method according to the modified feedstock of the 3rd embodiment of the present invention.
Fig. 5 has schematically shown the delayed coking method according to the modified feedstock of the 4th embodiment of the present invention.
Fig. 6 has schematically shown the delayed coking method according to the modified feedstock of the 5th embodiment of the present invention.
Embodiment
To on the basis of accompanying drawing and preferred embodiment thereof, describe according to of the present invention it is characterized in that with these biomass (14) and modified feedstock co-processing be used for that preparation comprises fuel gas and LPG (3), light naphtha (4), heavy naphtha (5), lightweight gas oil (6), matter gas oil (7) and from one or more the delayed coking method of product in the heavy gas oil (8) of coke.
Fig. 1 has schematically shown the delayed coking method according to prior art.
Fresh hydrocarbon charging (1) is supplied in the separation column (2), from wherein taking out described product.
To supply with in the stove (10) to cause thermally splitting from the bottom product (9) of this separation column (2).To send into coke drum (12) from the effluent (11) of this stove (10) then, finishing thermally splitting and coking, preparation coke and from the effluent (13) of this coke drum (12), it comprises light hydrocarbon, and it is sent to this separation column (2).
In first embodiment of the present invention, the method for charging modification schematically is presented among Fig. 2 in delayed coking unit, according to it, biomass (14) is added in the fresh feed (1).As can seeing, these biomass (14) are added in this fresh feed (1), prepare new logistics (1 '), it is supplied in the separation column (2), from wherein taking out described product.Use is in the 0.01%-80% scope, and preferably the biomass in the 0.5%-30% scope (14) are with respect to the volume percent of this fresh feed (1).
To supply with in the stove (10) to cause thermally splitting from the bottom product (9) of this separation column (2).Randomly this fresh feed (1) can be supplied with gravitation tank (15) or similar device, and then enter this stove (10).
To send into coke drum (12) from the effluent (11) of this stove (10) then, finishing thermally splitting and coking, preparation coke and from the effluent (13) of this coke drum (12), it comprises light hydrocarbon.Then this effluent (13) is sent to this separation column (2).
The another kind of possibility that has shown application of the present invention among Fig. 3 has wherein schematically shown second embodiment of the present invention, wherein in reaction or chilling phase process these biomass is added in this coke drum (12).Details is described below.
Fresh hydrocarbon charging (1) is supplied in the separation column (2), from wherein taking out described product.
To supply with in the stove (10) to cause thermally splitting from the bottom product (9) of this separation column (2).Randomly this fresh feed (1) can be supplied with gravitation tank (15) or similar device, and then enter this stove (10).To send into coke drum (12) from the effluent (11) of this stove (10) then, and in reaction or chilling phase process, biomass (14) are added in this coke drum (12), to finish thermally splitting and coking, preparation coke and from the effluent (13) of this coke drum (12), it comprises light hydrocarbon, then it is sent to this separation column (2).These biomass (14) with respect to the volume percent of this fresh feed (1) in the 0.01%-80% scope, preferably in the 0.5%-30% scope.
In the 3rd embodiment of the present invention shown in Fig. 4, schematically shown the method for charging modification in delayed coking unit.In this embodiment, as described below biomass (14) are added in the stove feeding line.
Fresh hydrocarbon charging (1) is supplied in the separation column (2), from wherein taking out described product.
Biomass (14) are added in the bottom product (9) from this separation column (2), produce new logistics (9 '), it is supplied with in stove (10) to cause thermally splitting.Equally in this embodiment, these biomass (14) with respect to the volume percent of this fresh feed (1) in the 0.01%-80% scope, preferably in the 0.5%-30% scope.Randomly this fresh feed (1) can be supplied with gravitation tank (15) or similar device, and then enter this stove (10), shown in dotted line.
To send into coke drum (12) from the effluent (11) of this stove (10) then, finishing thermally splitting and coking, preparation coke and from the effluent (13) of this coke drum (12), it comprises light hydrocarbon, then it is sent to this separation column (2).
Alternately, in the 4th embodiment of the present invention shown in Fig. 5, schematically shown the method for charging modification in delayed coking unit.In this embodiment, these biomass (14) are added in the outlet line from this stove.Be discussed in more detail below used program.
Fresh hydrocarbon charging (1) is supplied in the separation column (2), from wherein taking out described product.
To supply with in the stove (10) to cause thermally splitting from the bottom product (9) of this separation column (2).
Randomly this fresh feed (1) can be supplied with gravitation tank (15) or similar device, and then enter this stove (10), shown in dotted line.
Biomass (14) are added in the effluent (11) from this stove (10), produce new logistics (11 '), subsequently it is sent into coke drum (12), to finish thermally splitting and coking, preparation coke and from the effluent (13) of this coke drum (12), it comprises light hydrocarbon, then it is sent to this separation column (2).These biomass (14) with respect to the volume percent of this fresh feed (1) in the 0.01%-80% scope, preferably in the 0.5%-30% scope.
In addition, in the 5th embodiment of the present invention, in Fig. 6, presented and be used to use another kind of possibility of the present invention.In this possibility, these biomass (14) are added in the outlet line of this coke drum.This method is following carries out.Fresh hydrocarbon charging (1) is supplied in the separation column (2), from wherein taking out described product.
Will be from supplying with in the bottom product (9) of this separation column (2) in the stove (10) to cause thermally splitting.To send into coke drum (12) from the effluent (11) of this stove (10) then, finishing thermally splitting and coking, preparation coke and from the effluent (13) of this coke drum (12), it comprises light hydrocarbon.Biomass (14) are added in the effluent (13) of this coke drum (12), produce new logistics (13 '), it is sent to this separation column (2).
These biomass (14) with respect to the volume percent of this fresh feed (1) in the 0.01%-80% scope, preferably in the 0.5%-30% scope.
Embodiment
The present invention will obtain easier understanding and evaluation from following embodiment.
Yet these embodiment only with the representative of the scope of the present invention of opposing, never are used to limit the present invention.
Embodiment 1
In the delayed coking unit of pilot plant scale, handle former Oleum Gossypii semen.Furnace maintains 500 ℃, and the pressure at coke drum top is 2kgf/cm 2G.
We obtain in from the diesel range of coke 58% mass yield and 14% mass yield in from the heavy gas oil scope of coke.The mass yield of coke is 3.5%, gas be 18%.
Embodiment 2
Handle refined soybean oil in the delayed coking unit of pilot plant scale, furnace maintains 500 ℃, and the pressure at coke drum top is 2kgf/cm 2G.
We obtain in from the diesel range of coke 65% mass yield and 6% mass yield in from the heavy gas oil scope of coke.The mass yield of coke is 2.6%, gas be 17%.
Embodiment 3
The mixture of vacuum resid that the processing by the oil that obtains from Marlim field (PETROBRAS Bacia de Campos) of processing 90% obtains in the delayed coking unit of pilot plant scale and 10% former Oleum Gossypii semen.Furnace maintains 500 ℃, and the pressure at coke drum top is 2kgf/cm 2G.
We obtain in from the diesel range of coke 40% mass yield and 19% mass yield in from the heavy gas oil scope of coke.The mass yield of coke is 25%, gas be 9%.
As can seeing, although in its preferred embodiment, also described the present invention with representational embodiment, but be used in by biomass with hydrocarbon feed in delayed coking unit co-processing and the key concept of the present invention for preparing the method for bio oil is still kept in the characteristic aspect of its novelty, although wherein do not break away from the spirit and scope of the present invention shown in appended claim, those skilled in the art can imagine and put into practice therewith conceivable variation, improvement, change, adjusting and the replacement that the theme of reason everywhere conforms to.

Claims (11)

1. be used for that preparation comprises fuel gas and LPG (3), light naphtha (4), heavy naphtha (5), lightweight gas oil (6), matter gas oil (7) and from one or more the method for product in the heavy gas oil (8) of coke, it is characterized in that biomass (14) are added to and be used in the delayed coking unit and fresh hydrocarbon charging co-processing, comprise with the next stage:
-fresh hydrocarbon charging (1) is supplied in the separation column (2), from wherein taking out described product;
-will supply with in the stove (10) to cause thermally splitting from the bottom product (9) of this separation column (2);
-will send into coke drum (12) from the effluent (11) of this stove (10), finishing thermally splitting and coking, preparation coke and from the effluent that comprises light hydrocarbon (13) of this coke drum (12);
-will be sent to this separation column (2) from the effluent (13) of this coke drum (12).
2. the method that is used to prepare product of claim 1 is characterized in that described biomass (14) and fresh hydrocarbon charging (1) co-processing in delayed coking unit.
3. each the method that is used to prepare product in the claim 1 or 2, it is characterized in that described biomass (14) are selected from comprises following group: sugarcane bar, bagasse, castorseed cake, Exocarpium cocois (Cocos nucifera L), rice husk, soy material, castor seeds, Semen Brassicae campestris, coconut oil and Oleum Gossypii semen, the oil ﹠ fat of animal-origin, it can use separately or use as its mixture of arbitrary proportion.
4. each the method that is used to prepare product in the aforementioned claim is characterized in that described biomass (14) are added in the described fresh hydrocarbon charging (1) of described delayed coking unit.
5. each the method that is used to prepare product among the claim 1-4 is characterized in that in reaction or chilling phase process described biomass (14) being added in the described coke drum (12).
6. each the method that is used to prepare product among the claim 1-5 is characterized in that described biomass (14) are added in the described bottom product (9) from described separation column (2).
7. each the method that is used to prepare product among the claim 1-6 is characterized in that described biomass (14) are added in the described effluent (11) from stove (10).
8. each the method that is used to prepare product among the claim 1-7 is characterized in that described biomass (14) are added in the described effluent (13) from coke drum (12).
9. be used for that preparation comprises fuel gas and LPG (3), light naphtha (4), heavy naphtha (5), lightweight gas oil (6), matter gas oil (7) and from one or more the method for product in the heavy gas oil (8) of coke, it is characterized in that biomass (14) are added to and be used in the delayed coking unit and fresh hydrocarbon charging co-processing, comprise with the next stage:
-fresh hydrocarbon charging (1) supplied to gravitation tank (15) or similarly in the device, enter then in the stove (10) and be used for thermally splitting;
-will send into coke drum (12) from the effluent (11) of this stove (10), finishing thermally splitting and coking, preparation coke and from the effluent that comprises light hydrocarbon (13) of this coke drum (12);
-will be sent to this separation column (2) from the effluent (13) of this coke drum (12), from wherein taking out product.
10. each the method that is used to prepare product in the aforementioned claim, it is characterized in that these biomass (14) with respect to the volume percent of described fresh hydrocarbon charging (1) in the 0.01%-80% scope.
11. the method that is used to prepare product of claim 10, it is characterized in that these biomass (14) with respect to the volume percent of described fresh hydrocarbon charging (1) in the 0.5%-30% scope.
CN2009801282619A 2008-07-31 2009-07-29 Process for production of bio-oil by coprocessing of biomass in a delayed coking unit Pending CN102099438A (en)

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