CN103890145A - Pyrolysis of biomass in the production of biofuels - Google Patents

Pyrolysis of biomass in the production of biofuels Download PDF

Info

Publication number
CN103890145A
CN103890145A CN201280031107.1A CN201280031107A CN103890145A CN 103890145 A CN103890145 A CN 103890145A CN 201280031107 A CN201280031107 A CN 201280031107A CN 103890145 A CN103890145 A CN 103890145A
Authority
CN
China
Prior art keywords
feed material
coking
biomass
thermal treatment
metallic substance
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201280031107.1A
Other languages
Chinese (zh)
Inventor
J·D·埃利奥特
D·A·维德莱克
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Foster Wheeler Inc
Amec Foster Wheeler USA Corp
Original Assignee
Foster Wheeler USA Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Foster Wheeler USA Corp filed Critical Foster Wheeler USA Corp
Publication of CN103890145A publication Critical patent/CN103890145A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/02—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of cellulose-containing 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
    • C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
    • C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
    • 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
    • C10B55/02—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials
    • C10B55/04—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials
    • C10B55/08—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form
    • C10B55/10—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material with solid materials with moving solid materials in dispersed form according to the "fluidised bed" technique
    • 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
    • C10B57/045—Other carbonising or coking processes; Features of destructive distillation processes in general using charges of special composition containing mineral oils, bitumen, tar or the like or mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Coke Industry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Production of a biofuel from a feedstock that includes a solid biomass material such as lemna. Aquatic plants such as pre-processed or whole lemna serve as a rich source of lipids, carbohydrates, residual proteins, cellulose and other organic materials that have the potential to be converted to hydrocarbons. A hydrocarbon feedstock is fed into the coking process and reaction products generated from the thermal process are collected. A coke product has an isotropic structure.

Description

Biomass pyrolytic in biofuel preparation
The cross reference of related application
According to 35U.S.C § 119 (e) regulation, the application requires to enjoy the U.S. Provisional Patent Application sequence number No.61/500 submitting on June 23rd, 2011,250 rights and interests, and it is incorporated herein by reference in full, as set forth herein comprehensively.
Invention field
The raw material the present invention relates to from comprising solid biologic metallic substance is prepared biofuel composition.
Background of invention
Recently the demand with respect to the alternative fuel source of petroleum-based products has been given prominence in the expense increasing, the threat of shortage and the interruption of supply.Biofuel especially becomes the focus of alternative fuel.
The present invention proposes a kind of method of producing biofuel in refinery thermal treatment unit, and the method is passed through co-treatment biomass and distillate (distillates) and residual oil (residuals) from traditional refining process.
From any type renewable raw materials, produce fuel, namely obtain the special fuel of desired characteristic, all have associated particular problem.Therefore, need a kind of renewable types of feedstock can be effective to prepare the method for high-quality fuel.
Summary of the invention
According to one embodiment of the invention, give birth to the method for prepared product fuel by the delayed coking of raw material, refer in conventional delayed coking device solid biomass and fresh hydrocarbon charging co-treatment.
In one embodiment of the invention of request protection, the raw material of conventional delayed coking device comprises that hydrocarbon feed is such as petroleum residual oil and the solid biologic metallic substance or do not have with distillate.In certain embodiments of the invention, solid biologic metallic substance is derived from waterplant.For example, waterplant such as pretreated or complete Lemna is as the potential source of being rich in lipid, carbohydrate, residual protein, Mierocrystalline cellulose and other organic substances that is converted to hydrocarbon.The pre-treatment of Lemna comprises that biomass extract the material stream of rich in proteins before transforming in coker.The source that can be used for other solid biologic metallic substance of embodiment of the present invention comprises that botanical components such as alpine yarrow, xyloid material, oilseeds and animal source material are such as fat.The biomass in all kinds and source can be used in embodiment of the present invention.
In certain embodiments of the invention, solid biomass mixes in varing proportions with hydrocarbon residual oil, the coking in delayed coking device of the slurries of generation.Slurries can form or form in coke-drum in step of reaction in the fresh feed part of device.The amount of described solid biomass with respect to the volume percent of fresh feed in from 0.1% to 60% scope.In slurries, the ratio of biomass can increase according to the capacity of coker device and its ability of processing biomass material.
The simple description of accompanying drawing
Fig. 1 is the schematic diagram of delayed coking technique; And
Fig. 2 is the schema of processing biomass technique according to illustrative embodiments of the invention.
The detailed description of specific embodiments of the present invention
In one embodiment of this invention, use the delayed coking process of the slurries that comprise hydrocarbon and solid biologic metallic substance at the delayed coking device shown in Fig. 1, or other applicable refinery thermal treatment units, as carried out in viscosity breaking or thermal cracker.
In one embodiment of this invention, hydrocarbon charging is fed in coke making process by the bottom liquid pond of coker separation column.The point that separation column shifts out from it as various liquids and gases products, for example fuel gas and LPG, light naphthar, heavy naphtha, light gas oil, middle gas oil and heavy gas oil.To be fed in coker well heater from the bottoms of coker separation column, thereby heat cracking reaction is started.Then the effluent of coker well heater is sent to coke-drum, carry out thermally splitting and coking or carburizing reagent until complete therein, produce coke and the effluent being made up of light hydrocarbon (coking steam) from coke-drum, this effluent is sent to coker separation column.In certain embodiments, a part of condensed fluid recirculation be pumped to coker well heater together with charging.
In one embodiment of this invention, solid biologic metallic substance is mixed with the charging of residue hydrocarbon and is fed to coker separation column.
In another embodiment of the present invention, solid biologic metallic substance can directly add coke-drum in reaction or during quenching.
In another embodiment of the present invention, solid biologic metallic substance, preferably with slurries form, can directly add coker well heater feeding line or directly added coke-drum before heating.In other embodiments of the present invention, the not heating in advance and directly add coker well heater feeding line of solid biologic metallic substance.
Pulpous state biomass can heat and flash distillation after low-temperature heat stage by stage, the water being produced with reduction and the carrying capacity of acidic hydrocarbon, otherwise these material demands are processed in the major portion of coker separation column, coker well heater, coke-drum, separation column recovery system and oil refinery waste's treatment system.
Solid biomass amount of substance with respect to the weight percent of slurries rest part in from 0.1% to 60% scope.In one embodiment of this invention, the amount of solid biomass with respect to the preferred weight percent of slurries rest part in from 10% to 40% scope.In another embodiment of the present invention, the amount of solid biomass with respect to the preferred weight percent of slurries rest part in from 20% to 40% scope.In slurries, the ratio of biomass can be according to the volume change of coker device.Low capacity device can hold the biomass (in petroleum residual oil) of 5wt%-20wt%, but jumbo device can contain the solid biologic metallic substance (in slurries) of 40wt%-50wt%.
Because biomass are introduced in coker incoming flow with 0.1% to 60% scope, coking is carried out under normal temperature and normal pressure.In delayed coking device, heavy oil feed, for example vacuum residuum pumps into coker well heater with the pressure of approximately also preferred 300-4000kPa (approximately 44 to 580psig), and described charging is therein heated to the temperature of approximately 460 DEG C to approximately 530 DEG C.Then discharge and enter coke-drum, in coke-drum, be commonly lower pressure, so that volatile matter can be shifted out from top, described pressure is generally 65 to 1100kPa (about 10-58psig), preferably in the scope of 100-300kPa (approximately 10 to 160psig).The service temperature on general drum top is at approximately 405 DEG C to 460 DEG C.
An embodiment of the inventive method as shown in Figure 2.The flow chart description of Fig. 2 a kind of technique of biomass pyrolytic.In a step of described technique, be provided (step 102) containing biomass material, in later step (step 104), raw material is heat-treated.In certain embodiments of the invention, use delayed coking process (step 106) to heat-treat.In other embodiments of the present invention, use fluidized-bed process of coking (step 108) to heat-treat.
In the time using delayed coking process (step 106), in some embodiments of the present invention, incoming flow is heated to the temperature of 460-530 DEG C under 300 to 4000kPa pressure, under the pressure of 65-1100kPa, at the bulging top temperature of 405-460 DEG C, discharge and enter retard coke-drum through the material stream of heating subsequently.
While using fluidized-bed process of coking in the heat treatment step (step 108), enter fluidized-bed Coking Reactor at normal pressure to incoming flow being discharged at the temperature of the pressure of 400kPa and 480-565 DEG C.
Solid biomass generally starts to decompose at the temperature that is low to moderate 200 DEG C.But the stability of solid biomass can variation during pyrolytic process, because there is main reaction and this main reaction is absorbed heat in coke-drum.
In one embodiment of this invention, the biomass decomposition reaction under lesser temps produces reaction water and many chemical species that has potential value, comprises acetic acid.
Biomass decomposition reaction in delayed coking device at high temperature can affect all reaction masses in coke-drum.Entrance reactive material needs fully high temperature of reaction to overcome the decomposition thermo-negative reaction of biomass.This temperature is apparently higher than the required temperature of conventional coker, and depends on the amount of biomass in charging blend.This not only has impact to operation, also the specification of heating heat transfer equipment is had to impact, and heating heat transfer equipment is generally fired heater, to supply higher Standard Enthalpies.
One embodiment of this invention relates to the alternate configuration of co-processing biomass in delayed coking device, and wherein pre-reaction part is inner or outside at coker.Use coker inside or outside pre-reaction part to have following advantage:
A. from coker operation, remove a large amount of reaction water, simplify the processing of products obtained therefrom.
B., compared with operating with abiotic matter required in coker, reduce the impact of total heat enthalpy change.
C. for coker, remove and reclaim water-soluble acid constituents.If think that these components have commercial appeal and can reclaim separately.
D. from other coker current, separate that sour water can be simplified in delayed coking device or from corrosion and the processing of the common current of delayed coking device.
E. pre-reaction system can many different modes structures.Some in these are: (1) is removed and anhydrated and light constituent with hot petroleum residual oil slurrying and with simple receptacle flash distillation, and (2) are with hot petroleum residual oil slurrying and slough water and light constituent in Tower System.
Work embodiment
Can more easily understand and evaluate the present invention from embodiment described below.But these embodiment only think the representative of protection domain of the present invention, can not limit by any way the present invention.
In certain embodiments of the invention, dry Lemna biomass are as solid biologic metallic substance, and it has the following component (in wt%) shown in table 1, and it can change according to the pre-treatment degree after growth optimization and proteins extraction.
Table 1
Mineral substance Carbon Hydrogen Nitrogen Sulphur Oxygen
6.95 45.89 6.04 3.71 0.27 37.15
Lemna biomass are a kind of light and soft solids, and density is about 490kg/cm3.Can be granulated to load and transport to refinery so that dissolved water absorption minimizes and provide the simple and easy processing that minimizes dedusting.Biomass are containing lipid, carbohydrate, residual protein, Mierocrystalline cellulose and other organic substances, these materials seldom or can not cause the interest of factory of general oil refinery, except it can change into hydrocarbon, especially valuable liquid transportation fuels or chemical intermediate.
Hydrocarbon derived from mineral sources is mainly made up of organic compound, and this organic compound, such as carbon and hydrogen, also has the sulfur-bearing of variable quantity and containing nitrogen molecule and very small amount of oxygen, is conventionally less than 0.5%, and metal.Above-mentioned biomass analysis, compared with general delayed coking device petroleum residual oil raw material, demonstrates low-down sulphur, high nitrogen and metal and very high oxygen level.The hydrocarbon weight ratio (C: H) of biomass is 7.6, but is only 52% of gross weight.By contrast, the hydrogen richness that is fed to the general non-refinable crude residual oil of business delayed coking device is 8.5 to 11wt%, C: the rank of H ratio is 8.5 to 9.0.This ratio is obviously processed and is changed with the residual oil of raw material sources and delayed coking device upstream.By inquiry, the productive rate that the productive rate of the expection liquid hydrocarbon that conversion of biomass obtains in delayed coking device can obtain lower than conventional residual oil raw material.In addition, in delayed coking device, it is unique that complex biological organic solid compound changes into the not reaction of condensable gases, liquid and coke (coal tar), and the reaction that this reaction meets with in conventional coking than petroleum liquid residual oil, even complicated residual oil is more complicated.
Embodiment 1
Lemna biomass residue is through after proteins extraction, in delayed coking device pilot plant from different petroleum residual oil co-processing, with the principle evidence that provides Wood Adhesives from Biomass to become can be used for the liquid of factory of oil refinery, and how definite reaction is different from the information of conventional coking.This work is repeatedly carried out, and all relates to processing from business refinery obtaining the standard oil residual oil as baseline operation at every turn.In other operations, Lemna biomass are mixed with residual oil with the treatable various ratios of pilot plant equipment, and the slurries of generation carry out coking.Each operating and setting uses fixing baseline residue, namely starches the liquid vehicle of state.For liquid yield is maximized, each operation is carried out under the low pressure of 15psig, and zero circulation, namely without circulation.Charging and product are analyzed.Result is through assessment and analysis, and the clean yield structure of biomass is definite by subtracting each other.
Test with the slurries that biomass concentration in petroleum residual oil is 10% to 20%wt..This is the limit of pilot plant capacity.But in commercial apparatus, according to the capacity of device, be up to 40 or 50%wt or higher higher concentration be possible.
Following table 2 has shown coking result, wherein Lemna biomass with 10% with light vacuum residuum blend.
table 2
the productive rate & elementary composition of Lemna biomass coking product
Change and arrange and be similar from the result of different vacuum residuum co-processing gained.The change of total amount is owing to " disturb (noise) " that (1) causes due to the difference in producing, reclaim and analyzing; (2) reproducibility of charging and test of products and repeatability; (3) investigator makes low volume data and adjusts effort.
Lemna biomass are fully mixed with oil vacuum residuum.Approximately 100 to approximately 150 microns of the particle diameter average out to of biomass, tap density is about 490kg/cm 3.If by biomass granulating so that it produces less impact, more safety and transport easily to environment, use and crush and grind with the small-particle for the preparation of test.By being milled to less particle, such as the mean sizes of 50 microns, will improve mixing.
The principle that solid biomass is decomposed into gas, liquid product and coke by coking obtains valid certificates, that is to say and provides evidence for principle.Especially, do further processing in factory of oil refinery and produce a large amount of liquid products.
In one embodiment of this invention, the gas of generation is almost all CO 2, there is a small amount of hydrogen and light hydrocarbon (methane, ethane, ethene etc.).
During with the clean petroleum residual oil of coking, obtain general 8% to 10% compared with, in one embodiment of this invention, produced the light gas of the high per-cent that is greater than 20%.The biomass nitrogen content reaction of high per-cent forms ammonia.
Oil delayed coking device raw material relatively, the high biomass of oxygen level relatively show that principal reaction generates gas CO 2and water, and produce the coke with relative elevated oxygen level.The liquid product producing with respect to petroleum residual oil charging coking, described product liquid has the oxygen of high-content.But it is low that this value is compared with the total oxygen content in biomass, and use in operation from petroleum residual oil produce liquid diluting time, can alleviate the impact of for example hydrotreater of other refinery processes.
reaction
In oxygen and charging, coke forms component reaction, forms the coke with higher oxygen content, makes coke have higher isotropy.This discovery can be used by mixing limited, a small amount of biomass ratio, affects the fragility of special anode coke and the isotropy of hardness thereby improve.Duration of test is sneaked into the biomass of 10wt%, 20wt% in petroleum residual oil, and we can obviously affect the physical structure of coke.In the time that employing becomes known for preparing the petroleum residual oil of anode coke, the coke producing without any biomass in charging has the sponge quality that meets high-quality anode coke.In employing charging blend, contain the standby coke of 10% and 20% biomass-making very fine and close, present the low porosity consistent with height isotropy shot coke structure.React and can explain this phenomenon by the coke formation material in the biomass high-content oxygen compound and biological tar and the petroleum residual oil that discharge.
Although the present invention is described by its preferred embodiment and exemplary embodiments, instruct the present invention co-processing biomass and hydrocarbon feed in delayed coking device to describe in such a way with the key concept of the technique of producing biofuel herein, allow those skilled in the art carry out with the change that matches of technical theme of processing, improvement, variation, reorganization herein and substitute, and can not depart from the spirit and scope of the present invention, as represented in appended claim.

Claims (20)

1. in refinery thermal treatment unit, pass through the method for co-processing biomass-making for biofuel, comprise the steps:
Feed material is fed to thermal treatment unit, the mixture that wherein this feed material comprises hydrocarbon and solid biologic metallic substance;
This feed material of thermal treatment; And
Collect the reaction product being produced by this feed material thermal treatment.
2. the process of claim 1 wherein that solid biologic metallic substance is derived from plant-sourced, animal source or aquatic source.
3. the method for claim 2, wherein aquatic source is waterplant.
4. the method for claim 3, wherein waterplant is Lemna or derives from the solid residue of Lemna after proteins extraction.
5. the process of claim 1 wherein that the hydrocarbon in charging is petroleum residual oil and distillate.
6. the process of claim 1 wherein that solid biologic metallic substance exists with the concentration of 10wt%-20wt%.
7. the process of claim 1 wherein that solid biologic metallic substance exists with the concentration of 40wt%-50wt%.
8. the process of claim 1 wherein that solid biologic metallic substance exists with the concentration of 0.1wt%-60wt%.
9. the process of claim 1 wherein that thermal treatment unit is delayed coking device.
10. the process of claim 1 wherein that reactor product comprises carbonic acid gas, ammonia and acetic acid.
The method of 11. claims 4, wherein Lemna carried out pre-treatment to remove deproteinize before being introduced into charging.
12. the process of claim 1 wherein that feed material is fed in coker separation column.
13. the process of claim 1 wherein that feed material is fed directly to coke-drum.
14. the process of claim 1 wherein that feed material is fed directly to calorifier inlets.
The method of 15. claims, wherein feed material is heated before adding thermal treatment unit.
16. the process of claim 1 wherein that thermal treatment is delayed coking process.
17. the process of claim 1 wherein that thermal treatment is fluidized-bed process of coking.
The method of 18. claims 14, wherein process of coking is delayed coking process, wherein incoming flow is under 300-4000kPa, to be heated to the temperature of 460-530 DEG C at pressure, with after be that 65-1100kPa, temperature are at 400-475 DEG C, to discharge to enter to postpone in coke-drum through the material stream of heating at pressure.
The method of 17. claims 15, wherein process of coking is fluidized-bed process of coking, wherein incoming flow is that normal pressure to 400kPa, temperature is to discharge and enter in fluidized-bed Coking Reactor at 480-565 DEG C at pressure.
Prepare the method for isotropic cokes, comprise the following steps for 18. 1 kinds:
A) merging comprises the feed material of the mixture of hydrocarbon and solid biologic metallic substance, and
B) material of merging is heat-treated to prepare isotropic cokes.
The method of 19. claims 18, wherein isotropic cokes presents low porosity.
The method of 20. claims 18, wherein solid biologic metallic substance exists with 0.1wt% to 60wt% in feed material.
CN201280031107.1A 2011-06-23 2012-06-23 Pyrolysis of biomass in the production of biofuels Pending CN103890145A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201161500250P 2011-06-23 2011-06-23
US61/500250 2011-06-23
PCT/US2012/043906 WO2012178131A1 (en) 2011-06-23 2012-06-23 Pyrolysis of biomass in the production of biofuels

Publications (1)

Publication Number Publication Date
CN103890145A true CN103890145A (en) 2014-06-25

Family

ID=47360803

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201280031107.1A Pending CN103890145A (en) 2011-06-23 2012-06-23 Pyrolysis of biomass in the production of biofuels

Country Status (11)

Country Link
US (1) US20120325641A1 (en)
EP (1) EP2723833A1 (en)
CN (1) CN103890145A (en)
BR (1) BR112013032849A2 (en)
CA (1) CA2840051A1 (en)
CL (1) CL2013003678A1 (en)
DE (1) DE112012002578T5 (en)
ES (1) ES2482915B1 (en)
MY (1) MY177107A (en)
WO (1) WO2012178131A1 (en)
ZA (1) ZA201309579B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110548879A (en) * 2019-06-04 2019-12-10 北京化工大学 Preparation method and application of green synthetic novel iron-carbon material

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10202557B2 (en) * 2014-12-19 2019-02-12 The United States Of America, As Represented By The Secretary Of Agriculture Methods of producing calcined coke from bio-oil and calcined coke produced thereby
EP3636729B1 (en) 2018-10-10 2021-11-24 BDI Holding GmbH Method for the preparation of coker coal

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6168709B1 (en) * 1998-08-20 2001-01-02 Roger G. Etter Production and use of a premium fuel grade petroleum coke
US20090031615A1 (en) * 2007-08-01 2009-02-05 General Electric Company Integrated method for producing a fuel component from biomass and system therefor
CN101583695A (en) * 2006-12-22 2009-11-18 Ifp公司 Method for hydro-processing a mixture containing animal or vegetal oils and petroleum cuts by intermediate stripping
US20100176026A1 (en) * 2008-12-24 2010-07-15 Cole Kathryn Y Co-processing of diesel biofeed and heavy oil
US20100251615A1 (en) * 2009-04-07 2010-10-07 Gas Technology Institute Method for producing methane from biomass
US20100256428A1 (en) * 2009-04-07 2010-10-07 Gas Technology Institute Hydropyrolysis of biomass for producing high quality liquid fuels
WO2010124030A1 (en) * 2009-04-21 2010-10-28 Sapphire Energy, Inc. Methods of preparing oil compositions for fuel refining
US20110119996A1 (en) * 2010-01-29 2011-05-26 Enginuity Worldwide, LLC Composite biomass fuel compact
CN102099438A (en) * 2008-07-31 2011-06-15 巴西石油公司 Process for production of bio-oil by coprocessing of biomass in a delayed coking unit

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2687992A (en) * 1949-06-28 1954-08-31 Universal Oil Prod Co Conversion of heavy petroleums in a fluidized coking operation
GB768209A (en) * 1954-05-11 1957-02-13 Exxon Research Engineering Co Control of bogging in fluidized coking of heavy hydrocarbon oils
GB1481799A (en) * 1973-11-30 1977-08-03 Coal Ind Manufacture of coke
US4210518A (en) * 1977-01-24 1980-07-01 Exxon Research & Engineering Co. Hydrogen-donor coal liquefaction process
US4497637A (en) * 1982-11-22 1985-02-05 Georgia Tech Research Institute Thermochemical conversion of biomass to syngas via an entrained pyrolysis/gasification process
US4919793A (en) * 1988-08-15 1990-04-24 Mallari Renato M Process for improving products' quality and yields from delayed coking
US5174891A (en) * 1991-10-29 1992-12-29 Conoco Inc. Method for producing isotropic coke
US6187147B1 (en) * 1998-05-15 2001-02-13 Conoco Inc. Delayed coker unit furnace
US20020179493A1 (en) * 1999-08-20 2002-12-05 Environmental & Energy Enterprises, Llc Production and use of a premium fuel grade petroleum coke
US7160437B2 (en) * 2002-12-04 2007-01-09 Exxonmobil Research And Engineering Company Method for determining the source of fouling in thermal conversion process units
US20070129450A1 (en) * 2005-11-18 2007-06-07 Barnicki Scott D Process for producing variable syngas compositions
US8022259B2 (en) * 2008-05-30 2011-09-20 Uop Llc Slurry hydroconversion of biorenewable feedstocks
WO2010129724A2 (en) * 2009-05-05 2010-11-11 Anne Schwartz Efficient biomass fractionating system for an energy pulse crop
BR112012023444A2 (en) * 2010-03-17 2017-10-03 Pa Llc METHOD AND SYSTEM FOR PROCESSING AQUATIC SPECIES
US8603325B2 (en) * 2010-03-25 2013-12-10 Exxonmobil Research And Engineering Company Biomass oil conversion process

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6168709B1 (en) * 1998-08-20 2001-01-02 Roger G. Etter Production and use of a premium fuel grade petroleum coke
CN101583695A (en) * 2006-12-22 2009-11-18 Ifp公司 Method for hydro-processing a mixture containing animal or vegetal oils and petroleum cuts by intermediate stripping
US20090031615A1 (en) * 2007-08-01 2009-02-05 General Electric Company Integrated method for producing a fuel component from biomass and system therefor
CN102099438A (en) * 2008-07-31 2011-06-15 巴西石油公司 Process for production of bio-oil by coprocessing of biomass in a delayed coking unit
US20100176026A1 (en) * 2008-12-24 2010-07-15 Cole Kathryn Y Co-processing of diesel biofeed and heavy oil
US20100251615A1 (en) * 2009-04-07 2010-10-07 Gas Technology Institute Method for producing methane from biomass
US20100256428A1 (en) * 2009-04-07 2010-10-07 Gas Technology Institute Hydropyrolysis of biomass for producing high quality liquid fuels
WO2010124030A1 (en) * 2009-04-21 2010-10-28 Sapphire Energy, Inc. Methods of preparing oil compositions for fuel refining
US20110119996A1 (en) * 2010-01-29 2011-05-26 Enginuity Worldwide, LLC Composite biomass fuel compact

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110548879A (en) * 2019-06-04 2019-12-10 北京化工大学 Preparation method and application of green synthetic novel iron-carbon material

Also Published As

Publication number Publication date
ES2482915A2 (en) 2014-08-05
ES2482915R1 (en) 2014-10-28
DE112012002578T5 (en) 2014-08-07
EP2723833A1 (en) 2014-04-30
US20120325641A1 (en) 2012-12-27
ZA201309579B (en) 2015-09-30
CL2013003678A1 (en) 2014-06-20
MY177107A (en) 2020-09-07
CA2840051A1 (en) 2012-12-27
ES2482915B1 (en) 2015-07-03
WO2012178131A1 (en) 2012-12-27
BR112013032849A2 (en) 2017-02-21

Similar Documents

Publication Publication Date Title
Kan et al. Lignocellulosic biomass pyrolysis: A review of product properties and effects of pyrolysis parameters
Islam et al. Properties of sugarcane waste-derived bio-oils obtained by fixed-bed fire-tube heating pyrolysis
Yang et al. Intermediate pyrolysis of biomass energy pellets for producing sustainable liquid, gaseous and solid fuels
David et al. Pyrolysis of rapeseed oil cake in a fixed bed reactor to produce bio-oil
Chen et al. Investigation of Mannich reaction during co-liquefaction of microalgae and sweet potato waste
Zheng Pyrolysis oil from fast pyrolysis of maize stalk
JP2014534318A (en) Method for upgrading oil, fuel product, and hydrocarbon product fraction
Bhattacharjee et al. Pyrolysis of Alternanthera philoxeroides (alligator weed): Effect of pyrolysis parameter on product yield and characterization of liquid product and bio char
Duan et al. Non-catalytic hydropyrolysis of microalgae to produce liquid biofuels
US20080072476A1 (en) Process for producing coal liquids and use of coal liquids in liquid fuels
US10301549B2 (en) Process for depolymerizing coal to co-produce pitch and naphthalene
Canel et al. Hydropyrolysis of a Turkish lignite (Tunçbilek) and effect of temperature and pressure on product distribution
Conrad et al. Comparison of fast pyrolysis bio‐oils from straw and miscanthus
CN102453510B (en) Combined processing method of copyrolysis of heavy oil and coal
Luik et al. Upgrading of Estonian shale oil heavy residuum bituminous fraction by catalytic hydroconversion
CN103890145A (en) Pyrolysis of biomass in the production of biofuels
Liu et al. Fractional distillation of biocrude from hydrothermal liquefaction of microalgae: Upgrading of fuel properties
US20140336427A1 (en) Methods of and apparatuses for upgrading a hydrocarbon stream including a deoxygenated pyrolysis product
Aliyu et al. Microalgae for biofuel: Isothermal pyrolysis of a fresh and a marine microalga with mass and energy assessment
Luik et al. Transformations of biomass internal oxygen at varied pyrolysis conditions
CN102220166A (en) Delayed coking method
Liu et al. Investigation on the structure evolution and thermochemical conversion characteristics of lignite after different pretreatment
RU2378317C2 (en) Method of non-waste thermal processing of heavy oil residues mixed with solid fuel
Kakku et al. Co-processing of organic fraction from groundnut shell biocrude with VGO in FCC unit to produce petrochemical products
CN102453512B (en) Processing method for heavy oil and coal copyrolysis

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20140625

RJ01 Rejection of invention patent application after publication