CN117264642A - Graded biomass cracking process and device - Google Patents
Graded biomass cracking process and device Download PDFInfo
- Publication number
- CN117264642A CN117264642A CN202210309375.0A CN202210309375A CN117264642A CN 117264642 A CN117264642 A CN 117264642A CN 202210309375 A CN202210309375 A CN 202210309375A CN 117264642 A CN117264642 A CN 117264642A
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- Prior art keywords
- pyrolysis
- biomass
- biomass feedstock
- feedstock particles
- temperature
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- 239000002028 Biomass Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000008569 process Effects 0.000 title claims abstract description 19
- 238000005336 cracking Methods 0.000 title description 2
- 239000002245 particle Substances 0.000 claims abstract description 65
- 238000000197 pyrolysis Methods 0.000 claims abstract description 61
- 238000010438 heat treatment Methods 0.000 claims abstract description 53
- 238000001035 drying Methods 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 3
- 238000007669 thermal treatment Methods 0.000 claims 2
- 230000003247 decreasing effect Effects 0.000 claims 1
- 230000001419 dependent effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 4
- 239000012075 bio-oil Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007158 vacuum pyrolysis Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- 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
- C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
- C10B49/16—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
-
- 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
- C10B49/00—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated
- C10B49/16—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form
- C10B49/20—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form in dispersed form
- C10B49/22—Destructive distillation of solid carbonaceous materials by direct heating with heat-carrying agents including the partial combustion of the solid material to be treated with moving solid heat-carriers in divided form 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
- C10B57/08—Non-mechanical pretreatment of the charge, e.g. desulfurization
- C10B57/10—Drying
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Dispersion Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention provides a staged biomass pyrolysis process and apparatus wherein biomass feedstock particles (d 5o average particle size of at least 1 mm) are subjected to a basic heat treatment under anaerobic conditions. The heat treatment of the biomass feedstock particles includes a heat treatment drying step at a temperature in the range of 100 ℃ to 250 ℃. Then, the biomass feedstock particles are heated to a temperature in the range of 280 ℃ to 350 ℃ at a pre-pyrolysis heating location in the heat treatment system, maintained in the same temperature range for at least 5 seconds, and then moved from the pre-pyrolysis heating location to a pyrolysis heating location by a conveyor system, heated to above 350 ℃ for pyrolysis.
Description
Technical Field
The present invention relates to a process for pyrolysis of biomass feedstock, which finds particular, but not exclusive, application in biomass pyrolysis processes for producing renewable liquid, gaseous and solid fuels.
Background
Biomass pyrolysis refers to the thermal decomposition of biomass (e.g., plant material such as wood and bark) under substantially anaerobic conditions. Biomass is typically a mixture of hemicellulose, cellulose, lignin, and small amounts of other organics. These components typically pyrolyze or degrade at different rates, different mechanisms and pathways. One conventional example of biomass pyrolysis is the production of charcoal, wherein the primary product of pyrolysis is charcoal. Alternative biomass pyrolysis techniques provide a product that contains a significant amount of liquid after cooling. Such liquids are typically dark brown liquids having a calorific value of about half that of conventional fuel oils, and are commonly referred to as bio-oils. In general, bio-oil is the most valuable product in pyrolysis reactions because bio-oil can be stored relatively easily for later use, such as for heating and power generation, and is typically a homogeneous hydrophilic mixture of polar organics and water.
The rate and extent of decomposition of the biomass components depends on the process parameters of the pyrolysis reactor, such as the rate of heating of the biomass, the heating pattern of the biomass, and the residence time of the subsequent products. These process parameters, in turn, may also have an influence on the subsequent reaction of the product, for example by secondary reactions, cleavage (of higher molecular mass products) or condensation (of lower molecular mass products).
There are several different options for achieving biomass heating in a fast pyrolysis reactor. For example, ablative pyrolysis requires pressing and rapidly moving biomass particles against a heated surface, which allows the use of relatively large biomass particles. Or fluidized bed and circulating fluidized bed pyrolysis reactors transfer heat from a heat source to biomass particles through a conventional and conductive mixture. Since heat transfer must typically be performed quickly, fluidized bed pyrolysis reactors require the use of small biomass particles, typically not exceeding 3 mm. Another option is vacuum pyrolysis, where the heating rate may be relatively low, but application of vacuum may allow for rapid extraction of pyrolysis products, thereby simulating some of the effects of rapid pyrolysis.
Disclosure of Invention
The present invention provides a biomass pyrolysis process wherein biomass feedstock particles are substantially heat treated in the absence of oxygen to pyrolyze the biomass feedstock particles, wherein the heat treatment of the biomass feedstock particles comprises a step wherein at least 50% of the mass of the biomass feedstock particles is heated to a temperature in the range of 280 ℃ to 350 ℃, maintained in the same temperature range for at least 5 seconds, and then heated to above 350 ℃ to effect pyrolysis, the biomass feedstock particles having a d50 average particle size of at least 1 mm, wherein d50 represents a number length average particle size such that 50% of the particle volume is smaller than the particle size of diameter d50 and 50% of the particle volume is greater than the particle size of diameter d 50. By this means the tar content of the pyrolysis product can be reduced. Wherein lignin is formed from uncontrolled condensation products in most pyrolysis processes, especially in most pyrolysis processes.
In another aspect, the present invention provides a biomass pyrolysis process wherein biomass feedstock particles are heat treated in the absence of oxygen to pyrolyze the biomass feedstock particles, wherein the heat treatment of the biomass feedstock particles comprises a step wherein at least a portion of each biomass feedstock particle is heated to a temperature in the range of 280 ℃ to 350 ℃, maintained in the same temperature range for at least 5 seconds, and then heated to above 350 ℃ to pyrolyze the biomass feedstock particles, the biomass feedstock particles having a d50 average particle size of at least 1 mm.
Preferably, in this second aspect, the portion of each particle whose temperature is controlled in the range of 280 ℃ to 350 ℃ is an outer portion of each particle. The depth outside each particle will typically vary depending on the time the particle is held in the temperature range of 280 ℃ to 350 ℃. Preferably, the depth extends substantially to the centre of the particle so that the whole particle is substantially within the desired temperature range.
In a third aspect, the present invention provides a biomass pyrolysis apparatus for thermally treating biomass feedstock particles in the substantial absence of oxygen to pyrolyse the biomass feedstock particles, means for providing a pre-pyrolysis heating station for heating the biomass feedstock particles to a temperature in the range 280 ℃ to 350 ℃ and maintaining the temperature of the biomass feedstock particles in the range 280 ℃ to 350 ℃ for at least 5 seconds, the apparatus further providing a pyrolysis heating station for subsequently heating the biomass feedstock particles above 350 ℃ for pyrolysis.
The biomass feedstock particles are preferably subjected to a heat treatment drying step at a temperature of from 100 ℃ to 250 ℃ and then reheated to a temperature of from 280 ℃ to 350 ℃. Thus, the heat treatment schedule preferably has at least three distinct phases: a first preheating and heating stage, a second preheating and heating stage and a pyrolysis and heating stage. Preferably, the biomass feedstock particles are subjected to the heat treatment drying step at a temperature in the range of 100 ℃ to 250 ℃ for a time sufficient to allow at least 50% of the mass of the particles to undergo the heat treatment drying step (and preferably at least 60%, at least 70%, at least 80% or at least 90% of the mass of the particles subjected to the heat treatment drying step) to reach a temperature of at least 100 ℃. (more preferably, at least 110 ℃, at least 120 ℃, at least 130 ℃, at least 140 ℃, at least 150 ℃, at least 160 ℃, at least 170 ℃, at least 180 ℃, at least 190 ℃, or at least 200 ℃). Of course, this depends on the particle size. Preferably, however, the time is at least 1 second, more preferably at least 5 seconds, more preferably at least 10 seconds, at least 20 seconds or at least 30 seconds.
First, the biomass feedstock particles may be temperature soaked at each fixed temperature stage and the average temperature of the biomass mass may also vary at each heating stage. Thus, during the pre-pyrolysis heating stage, the average temperature of the biomass mass may rise, provided that it remains within the desired range for the desired time. However, the average temperature of the biomass mass is faster than the temperature change rate of the heat treatment drying stage and the pre-pyrolysis heating stage between the heat treatment drying stage and the pre-pyrolysis heating stage. Similarly, it is preferred that the average temperature of the biomass mass is faster between the preheat and pyrolysis stages than the rate of temperature change during the preheat and pyrolysis stages. In this way, a staged heat treatment plan is provided for the biomass. This provides the advantage of a relatively long residence time of the biomass within the temperature range providing technical advantages and a relatively short residence time at the temperature providing technical disadvantages.
Drawings
FIG. 1 is a schematic layout of a pyrolysis reactor arrangement according to one embodiment of the invention
Fig. 2 is a schematic layout showing a pyrolysis reactor device according to another embodiment of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Referring to fig. 1, an embodiment of the present invention provides for a first heating stage in the apparatus, with the first fluidized bed reactor 12 carrying a heat carrier (not shown) heated to 200 ℃. The heating phase corresponds to a first preheating and de-heating phase. A biomass feedstock (not shown) is fed into the first fluidized bed reactor 12 through inlet 14. The gaseous product from the first fluidized bed reactor 12 (i.e., the gaseous product of heating the biomass feedstock at 200 ℃ or near 200 ℃) is extracted at the first reactor gaseous product outlet 16. The gaseous product of the first reactor may be rich in water but may still have a useful heating value. In this case, the gaseous product of the first reactor may be used to heat the heat carrier used in the one or more reactors. At the bottom of the first reactor 12 is an outlet 18 for transporting the treated biomass feedstock from the first reactor 12 to a second reactor 20. The material input into the second reactor 20 is controlled by the second reactor inlet 22. The material may be conveyed from the first reactor 12 to the second reactor 20 by gravity alone, or may be conveyed by a screw conveyor in addition or as well.
The heat carrier used in the first reactor is preferably recycled for further use in the apparatus, most preferably for further use in the first reactor, in order to minimize the amount of reheating required. However, some of the heat carrier used in the first reactor may be transferred to the second reactor. The heat carrier may be, for example, char, sand, and steel. Some or all of the heat carrier may be recovered or transferred, depending on the process required to separate it from the feedstock. The second reactor 20 is also a fluidized bed reactor, but differs from the first reactor 12 in that it is operated at 300 ℃. This corresponds to a second pre-pyrolysis stage, whereby the biomass feedstock is maintained in the second reactor 20 for a time sufficient to achieve a biomass feedstock particle mass of at least 50% to about 300 ℃. The time required for this depends on the particle size of the feedstock.
Fig. 2 illustrates an alternative embodiment of the present invention. A mixing drum reactor apparatus 50 is provided herein. Mixing paddles 52, 54, 56, 58 are used for mixing biomass feedstock 53 and heat carrier 55. They rotate about the shaft 51. In fig. 2, the biomass feed is typically conveyed in a left to right direction. A slight inclination of the reactor axis may help to achieve this, but this is not required. It can be seen that figure 2 provides four heating stages, 200 ℃, 300 ℃, 400 ℃ and 500 ℃, respectively. They correspond to the first (200 ℃) pre-pyrolysis stage, the second (300 ℃) pre-pyrolysis stage, the first (400 ℃) pyrolysis stage and the second (500 ℃) pyrolysis stage described in fig. 1.
Claims (7)
1. A staged biomass pyrolysis process and device are characterized in that: wherein the biomass feedstock particles are subjected to a substantially heat treatment in the absence of oxygen, wherein the heat treatment of the biomass feedstock particles comprises a step in which at least 50% of the mass of the biomass feedstock particles is heated to a temperature in the range of 280 ℃ to 350 ℃, maintained in the same temperature range for at least 5 seconds, and then heated to above 350 ℃ for pyrolysis; the biomass feedstock particles have a d50 average particle size of at least 1 mm, wherein d50 represents a number length average particle size such that 50% of the particle volume is smaller than the particle size of d50, and 50% of the particle volume is larger than the particle size of d 50.
2. A staged biomass pyrolysis process and apparatus as claimed in claim 1, wherein the biomass feedstock particles are subjected to a heat treatment drying step at a temperature in the range of 100 ℃ to 250 ℃ and then heated to a temperature in the range of 280 ℃ to 350 ℃.
3. A staged biomass pyrolysis process and apparatus as claimed in claim 1, wherein in the step of heating at least 50% by mass of the biomass feedstock particles to a temperature in the range 280 ℃ to 350 ℃ and maintaining the same temperature range for a time t280-350 the following relationship is satisfied: t280-350 is equal to or larger than Cd50; in this formula, d50 is the number length average particle size in meters and C is a constant, at least 5000 seconds per meter.
4. A staged biomass pyrolysis process and apparatus as claimed in claim 1, wherein the biomass feedstock particles are heated to a temperature of 280 ℃ to 350 ℃ at a pre-pyrolysis heating location in the thermal treatment system, and subsequently heated to a temperature above 350 ℃ to effect pyrolysis at the pyrolysis heating location in the thermal treatment system.
5. The biomass pyrolysis process of claim 4, wherein biomass feedstock particles are moved between a pre-pyrolysis heating location and a pyrolysis heating location by a conveyor system; the biomass feedstock particles move substantially between the pre-pyrolysis heating location and the pyrolysis heating location without decreasing the temperature; the conveying system is a screw conveyor.
6. The biomass pyrolysis process and apparatus of claim 4, wherein the conveyor system conveys the biomass feedstock particles at a substantially uniform rate, and the residence time of the biomass feedstock particles at the pre-pyrolysis heating location and the pyrolysis heating location is dependent on the spatial extent of the pre-pyrolysis heating location and the pyrolysis heating location, and the conveying rate of the biomass feedstock particles.
7. A staged biomass pyrolysis process and apparatus as claimed in claim 1, wherein at least 50% by mass of the biomass feedstock particles are maintained within the same temperature range for at least 5 seconds at a temperature in the range of 280 ℃ to 320 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210309375.0A CN117264642A (en) | 2022-03-28 | 2022-03-28 | Graded biomass cracking process and device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210309375.0A CN117264642A (en) | 2022-03-28 | 2022-03-28 | Graded biomass cracking process and device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117264642A true CN117264642A (en) | 2023-12-22 |
Family
ID=89220116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210309375.0A Pending CN117264642A (en) | 2022-03-28 | 2022-03-28 | Graded biomass cracking process and device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117264642A (en) |
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2022
- 2022-03-28 CN CN202210309375.0A patent/CN117264642A/en active Pending
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