CN116554902A - Method for preparing deoxidized oil and carbon material with high specific surface area by using energy-saving biomass - Google Patents
Method for preparing deoxidized oil and carbon material with high specific surface area by using energy-saving biomass Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 9
- 238000000197 pyrolysis Methods 0.000 claims abstract description 165
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 230000004913 activation Effects 0.000 claims abstract description 57
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 41
- 239000007789 gas Substances 0.000 claims abstract description 39
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 36
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 36
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000000571 coke Substances 0.000 claims abstract description 23
- 239000003546 flue gas Substances 0.000 claims abstract description 22
- 239000000443 aerosol Substances 0.000 claims abstract description 20
- 238000005265 energy consumption Methods 0.000 claims abstract description 9
- 238000001833 catalytic reforming Methods 0.000 claims abstract description 7
- 238000004064 recycling Methods 0.000 claims abstract description 5
- 230000006835 compression Effects 0.000 claims description 20
- 238000007906 compression Methods 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000001994 activation Methods 0.000 description 35
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- 239000003610 charcoal Substances 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000010902 straw Substances 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 241000609240 Ambelania acida Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006057 reforming reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- -1 sawdust Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
Classifications
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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
- C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting 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
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
-
- 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
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Processing Of Solid Wastes (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses an energy-saving method for preparing deoxidized oil and a carbon material with high specific surface area. The method comprises the treatment steps of pressure pyrolysis, in-situ activation, one-step activation, trapping, conversion, deoxidation, incineration and the like. And carrying out pressure pyrolysis on biomass in different temperature sections in a pressure pyrolysis unit to obtain pyrolysis coke, pyrolysis vapor and pyrolysis volatile matters, wherein the pyrolysis vapor is used for preparing activated carbon with high specific surface area through in-situ activation of the pyrolysis coke, and activated synthesis gas is obtained. And introducing active component aerosol into the active carbon with high specific surface area, and simultaneously carrying out catalytic reforming reaction of one-step activation, trapping, conversion and deoxidation on biomass pyrolysis volatile matters to obtain the biomass carbon-based catalyst, the synthesis gas and the high-quality deoxidized oil. The activated synthesis gas and the synthesis gas are burned in the burning unit to recover energy, the energy is supplied to the pressurizing pyrolysis unit and the activation unit, and finally low-temperature flue gas is discharged. The method not only solves the problem of high biomass recycling energy consumption, but also provides a technical scheme for improving the quality of biomass pyrolysis products.
Description
Technical field:
the invention relates to the technical field of biomass pyrolysis and quality improvement of pyrolysis products, in particular to a method for preparing deoxidized oil and a carbon material with a high specific surface area by using energy-saving biomass.
The background technology is as follows:
biomass renewable resources occupy an important role in energy structures, and the proportion of biomass renewable resources in total energy consumption structures rises year by year. Biomass pyrolysis has the problems of more pollutant components in crude pyrolysis gas, high oxygen content in pyrolysis oil, poor quality of pyrolysis coke, high pyrolysis energy consumption and the like, and the quality of biomass pyrolysis products is required to be improved and the energy consumption is reduced.
The invention comprises the following steps:
aiming at the problem that biomass cannot be effectively recycled with low energy consumption in the prior art, the invention provides a method for preparing deoxidized oil and a carbon material with high specific surface area by using energy-saving biomass.
The invention aims to provide a method for preparing deoxidized oil and a carbon material with a high specific surface area by using energy-saving biomass, which comprises the following steps of sequentially carrying out step-by-step pressurized pyrolysis, activation, trapping conversion and incineration on biomass in different temperature sections according to larger difference of thermal stability of different components of the biomass to obtain a carbon-based catalyst (10), deoxidized oil (12) and low-temperature flue gas (13), and specifically comprises the following steps: respectively feeding biomass (1) into a primary compression pyrolysis unit and a secondary compression pyrolysis unit to carry out compression pyrolysis at different temperature sections to obtain pyrolysis vapor (6), pyrolysis volatile matters (2)/(3) and pyrolysis coke (4)/(5); the pyrolysis steam (6) respectively carries out in-situ activation on the pyrolysis coke (4)/(5) through an in-situ activation unit to obtain activated carbon (7) with high specific surface area and activated synthesis gas (8); the high specific surface area activated carbon (7) enters a one-step activation, trapping, conversion and deoxidization unit and pyrolysis volatile matters (2) and (3) are subjected to activation, catalysis and reforming reaction in an active component aerosol (9) atmosphere to obtain a carbon-based catalyst (10), synthesis gas (11) and deoxidized oil (12); the activated synthesis gas (8) and the synthesis gas (11) enter an incineration unit to be incinerated to provide energy for a primary compression pyrolysis unit, a secondary compression pyrolysis unit and an in-situ activation unit, low-temperature flue gas (13) is obtained, and biomass low-energy consumption recycling is achieved.
According to the invention, according to the fact that different components of biomass have larger thermal stability difference, biomass is subjected to pyrolysis treatment according to different temperature sections to obtain pyrolysis vapor, pyrolysis gas, condensed pyrolysis oil and pyrolysis coke. The condensed pyrolysis oil and the pyrolysis coke are main products of biomass pyrolysis, and the quality improvement and recycling of the main products determine the economy of biomass pyrolysis. The biomass pyrolysis vapor is used for preparing the activated carbon with high specific surface area through in-situ activation of pyrolysis coke, is used for adsorption treatment of heavy metals in sewage and VOC in air, and can also be used in the fields of catalysts, energy storage materials and the like. The active component aerosol is used for carrying out one-step activation, trapping, conversion and deoxidation on the active carbon with high specific surface area and the pyrolysis volatile component, and the obtained carbon-based catalyst can be used for improving the quality of biomass oil.
Preferably, pyrolysis water vapor (6) obtained by the primary compression pyrolysis unit and the secondary compression pyrolysis unit is collected into the same container; the biomass is subjected to pressurized pyrolysis, in-situ activation and one-step activation, trapping, conversion and deoxidation to obtain deoxidized oil (12) and a carbon-based catalyst (10), and the deoxidized oil and the carbon-based catalyst are respectively collected into the same container.
Preferably, the biomass is subjected to primary/secondary pressurized pyrolysis unit, the flow rate of nitrogen is 100-200 mL/min, the pressure is 0.1-35 MPa, the temperature is 150-200 ℃ and maintained for 0.5-1.0 h, pyrolysis vapor (6) is obtained, then the temperature is raised to 500-650 ℃ and maintained for 0.8-1.5 h, and pyrolysis volatile components (2)/(3) and pyrolysis coke (4)/(5) are obtained.
Preferably, pyrolysis vapor (6) enters an in-situ activation unit III/IV to be subjected to in-situ activation high temperature heat Jie Jiao (4)/(5) to obtain activated carbon (7) with high specific surface area and activated synthesis gas (8), the activation pressure in the in-situ activation unit III/IV is 0.1-35 MPa, the activation temperature is 550-1000 ℃, the activation time is 0.5-1.0 h, and the mass ratio of the pyrolysis vapor (6) to the pyrolysis coke (4)/(5) is 0.1-0.8. The low temperature flue gas (13) also provides energy for the in situ activation unit III/IV.
The pyrolysis vapor obtained by the secondary pressurized pyrolysis unit is used as a reactant of the in-situ activation unit III, and the pyrolysis vapor obtained by the primary pressurized pyrolysis unit is used as a reactant of the in-situ activation unit IV, so that a product obtained by the pyrolysis reaction is fully utilized.
Preferably, the specific surface area of the activated carbon (7) with high specific surface area obtained by in-situ activation is 100-1200 m 2 Ash concentration is 0.1-2.0 wt.%/g.
Preferably, the activated carbon (7) with high specific surface area and biomass pyrolysis volatile components (2)/(3) are introduced into an activated trapping conversion deoxidizing unit in the atmosphere of an active component aerosol (9) to perform an activated catalytic reforming reaction, so as to obtain the carbon-based catalyst (10), the synthesis gas (11) and the deoxidized oil (12), wherein the reaction temperature is 550-900 ℃, the reaction pressure is 0.1-35 MPa, the reaction time is 0.5-2.0 h, the mass ratio of the pyrolysis volatile components (2)/(3) to the high specific surface area active carbon (7) is 0.5-5.0, the mass concentration of the active components in the active component aerosol is 10-50%, and the mass ratio of the active component aerosol to the high specific surface area active carbon is 0.01-0.20. Further preferably, the reaction temperature is 600-650 ℃, the reaction time is 1.0-1.5 h, the mass ratio of the pyrolysis volatile component (2)/(3) to the high specific surface area active carbon (7) is 1.5-3.0, the mass concentration of the active component in the active component aerosol is 10-15%, and the mass ratio of the active component aerosol (9) to the high specific surface area active carbon (7) is 0.05-0.10.
Preferably, said active ingredient aerosolThe active component is metal oxide including CaO and Fe 2 O 3 、MaO、K 2 O and BaO.
Preferably, the activated synthesis gas (8) obtained by in-situ activation and the synthesis gas (11) obtained by activation, trapping, conversion and deoxidation are incinerated to obtain low-temperature flue gas (13), the low-temperature flue gas is used for supplying energy to the pressurized pyrolysis unit and the in-situ activation unit, and the incineration temperature is 700-1000 ℃.
Preferably SO in the low temperature flue gas (13) x (sulfur oxide) and NO x The emission concentration of (nitrogen oxides) is respectively lower than 20mg/m 3 And 30mg/m 3 . Further preferably, SO x The discharge concentration is 0.1-15 mg/m 3 ，NO x The discharge concentration is 0.1-20 mg/m 3 。
The high specific surface area activated carbon (7) and metal oxide aerosol obtained by pyrolysis volatile components (2)/(3) and in-situ activation enter a one-step activation, trapping and conversion deoxidization unit V at the same time, and quality improvement is carried out on the pyrolysis volatile components (2)/(3) and the high specific surface area activated carbon (7) to obtain a carbon-based catalyst (10), synthesis gas (11) and deoxidized oil (12). The specific surface area of the carbon-based catalyst (10) is 100-1000 m 2 Ash concentration is 0.1-3.0 wt.%/g. CO in the received synthesis gas (11) 2 The concentration is 1-10%, NO x (nitrogen oxide) concentration of 0.01% -0.09%, SO x The concentration of (sulfur oxide) is 0.01% -0.09%, the concentration of hydrogen is 5% -20%, the concentration of methane is 20% -45%, the concentration of CO is 15% -35%, and the concentration of oxygen in deoxidized oil (12) is 0.1% -1.0%.
Compared with the prior art, the invention has the following advantages: the method for preparing the deoxidized oil and the carbon material with high specific surface area is used for preparing the deoxidized oil with low concentration, the carbon-based catalyst and the low-temperature flue gas, and simultaneously reduces the energy consumption of biomass pyrolysis treatment. The deoxidized oil prepared by the invention has low oxygen content concentration, and can be used as liquid fuel to replace fossil fuel. The carbon-based catalyst prepared by the method has large specific surface area, uniform particles and good quality, and can be used for O/S/N removal catalyst of biomass pyrolysis oil. The low-temperature flue gas discharged by the invention has low pollutant discharge concentration. The invention not only solves the problem of high energy consumption of biomass treatment, but also provides a way for recycling biomass, and has wide application prospect.
Description of the drawings:
FIG. 1 is a schematic diagram of the process of preparing deoxidized oil and carbon material with high specific surface area from energy-saving biomass.
The specific embodiment is as follows:
the following examples are further illustrative of the invention and are not intended to be limiting thereof.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention. Unless otherwise indicated, the experimental materials and reagents herein are all commercially available products conventional in the art. The biomass provided by the invention comprises straw, sawdust, bagasse, rice chaff and the like, and the biomass is preferably corn straw in the following embodiments. The particle size of the crushed biomass is more than 100 meshes.
Example 1
Referring to fig. 1, according to the method for preparing deoxidized oil and carbon deposit material with high specific surface area by using energy-saving biomass, biomass is subjected to fractional pressure pyrolysis, activation, trapping, conversion and incineration in different temperature sections according to the large difference of thermal stability of different components of biomass, so as to obtain a carbon-based CaO catalyst, deoxidized oil (12) and low-temperature flue gas (13). The method specifically comprises the following steps:
(1) According to the fact that the difference of thermal stability of different components of biomass is large, the crushed biomass is sent to a first-stage pressurized pyrolysis unit I to carry out pressurized pyrolysis at different temperature sections, and pyrolysis volatile matters (2), pyrolysis vapor (6) and pyrolysis coke (4) are obtained. The height of the biomass filling material is not more than 3/5 of the furnace body of the primary pressurized pyrolysis unit I. First, pyrolysis steam (6) was obtained by maintaining the flow rate of nitrogen at 200mL/min, the pressure at 1.0MPa, and the temperature at 200℃for 0.5 hours. Then, the temperature was raised to 600℃and maintained for 1.0h, to obtain pyrolysis volatiles (2) and pyrolysis char (4).
(2) According to the fact that the thermal stability difference of different components of biomass is large, the crushed biomass is crushedAnd the biomass is sent into a secondary pressurized pyrolysis unit II to carry out pressurized pyrolysis at different temperature sections. The height of the biomass filler is not more than 3/5 of the furnace body of the secondary pressurized pyrolysis unit. First, pyrolysis steam (6) was obtained by maintaining the flow rate of nitrogen at 200mL/min, the pressure at 1.0MPa, and the temperature at 200℃for 0.5 hours. And (3) introducing pyrolysis steam (6) into an in-situ activation unit III, and in-situ activating pyrolysis coke (4) for 1.0h at 600 ℃ and 1.0MPa to obtain high specific surface area activated carbon (7) and activated synthesis gas (8). The mass ratio of the pyrolysis water vapor (6) to the pyrolysis coke (4) is 0.5. The specific surface area of the activated carbon with high specific surface area is 800m 2 /g。
(3) The temperature of the secondary pressurized pyrolysis unit II is raised to 600 ℃ and maintained for 1.0h, so as to obtain pyrolysis volatile components (3) and pyrolysis coke (5). The pyrolysis volatile component (3), 13.0% CaO aerosol at 300 ℃ and high specific surface area active carbon (7) enter a one-step activation, trapping and conversion deoxidization unit V at the same time, catalytic reforming reaction is carried out at 600 ℃ for 2.0h, the mass ratio of the high specific surface area active carbon (7) to the pyrolysis volatile component (3) is 3.0, and the mass ratio of CaO aerosol to the high specific surface area active carbon (7) is 0.05, so that a biomass charcoal-based CaO catalyst, synthesis gas (11) and deoxidized oil (12) are obtained. The specific surface area of the biomass charcoal-based CaO catalyst is 500m 2 The ash concentration per gram was 1.0wt.%, and the oxygen content of the deoxygenated oil (12) was 0.5%. CO in the synthesis gas (11) 2 Concentration of 2.0%, NO x Concentration of 0.03%, SO x The concentration was 0.02%, the hydrogen concentration was 8%, the methane concentration was 30%, and the CO concentration was 28%.
(4) The activated synthesis gas (8) and the synthesis gas (11) are introduced into an incineration unit VI, low-temperature flue gas (13) is obtained by incineration at 700 ℃, and heat energy generated by the incineration is supplied to a primary compression pyrolysis unit I, a secondary compression pyrolysis unit II and an in-situ activation unit III. SO in the discharged low-temperature flue gas (13) 2 The discharge concentration was 10mg/m 3 ，NO x The discharge concentration was 15mg/m 3 。
Example 2
Referring to fig. 1, according to the method for preparing the deoxidized oil and the carbon-based catalyst by using the energy-saving biomass, the biomass is subjected to fractional pyrolysis, activation, trapping, conversion and incineration in different temperature sections according to the fact that the thermal stability difference of different components of the biomass is large, so that the carbon-based MgO catalyst, the deoxidized oil (12) and the low-temperature flue gas (13) are obtained. The method specifically comprises the following steps:
(1) According to the fact that the thermal stability difference of different components of biomass is large, the crushed biomass is sent to a secondary pressurized pyrolysis unit II to carry out pyrolysis at different temperature sections, and pyrolysis volatile matters (3), pyrolysis vapor (6) and pyrolysis coke (5) are obtained. The height of the biomass filler is not more than 2/3 of the furnace body of the secondary pressurized pyrolysis unit II. First, pyrolysis steam (6) was obtained by maintaining the flow rate of nitrogen at 150mL/min, the pressure at 2.0MPa, and the temperature at 150℃for 1.0 h. Then, the temperature was raised to 650℃and maintained for 0.8 hours, to obtain a pyrolysis volatile (3) and pyrolysis char (5).
(2) According to the fact that the thermal stability difference of different components of biomass is large, the crushed biomass is sent to a first-stage pressurized pyrolysis unit I to carry out pyrolysis at different temperature sections. The height of the biomass filler is not more than 2/3 of the furnace body of the primary pressurized pyrolysis unit. First, pyrolysis steam (6) was obtained by maintaining the flow rate of nitrogen at 150mL/min, the pressure at 2.0MPa, and the temperature at 150℃for 1.0 h. And (3) introducing pyrolysis steam (6) into an in-situ activation unit IV, and in-situ activating pyrolysis coke (5) for 0.5h at 600 ℃ and 2.0MPa to obtain high specific surface area activated carbon (7) and activated synthesis gas (8). The specific surface area of the activated carbon (7) with high specific surface area is 600m 2 /g。
(3) The temperature of the primary pressurized pyrolysis unit I was raised to 650 ℃ and maintained for 0.8h to obtain pyrolysis volatiles (3) and pyrolysis char (5). The pyrolysis volatile component (3), 15.0% MgO aerosol at 250 ℃ and high specific surface area active carbon (7) enter a one-step activation, trapping, conversion and deoxidization unit V at 650 ℃ for catalytic reforming reaction for 0.5h, wherein the mass ratio of the high specific surface area active carbon to the pyrolysis volatile component (3) is 1.5, and the mass ratio of MgO aerosol to the high specific surface area active carbon is 0.08, so as to obtain the carbon-based MgO catalyst, the synthetic gas (11) and the deoxidized oil (12). The specific surface area of the carbon-based MgO catalyst is 450m 2 The ash concentration per gram was 2.0wt.%, and the oxygen content of the deoxygenated oil (12) was 0.9%. CO in the synthesis gas (11) 2 Concentration of 5.0%, NO x Concentration of 0.09%, SO x The concentration is 0.06%, the hydrogen concentration is 10%, the methane concentration is 35%, and the CO concentration is20%.
(4) The activated synthesis gas (8) and the synthesis gas (11) are introduced into an incineration unit VI, low-temperature flue gas (13) is obtained by incineration at 750 ℃, and heat energy generated by the incineration is supplied to a primary compression pyrolysis unit I and a secondary compression pyrolysis unit II. SO in the discharged low-temperature flue gas (13) 2 The discharge concentration was 16mg/m 3 ，NO x The discharge concentration was 10mg/m 3 。
Example 3
Referring to fig. 1, according to the method for preparing the deoxidized oil and the carbon-based catalyst by using the energy-saving biomass, biomass is subjected to fractional pyrolysis, activation, trapping, conversion and incineration in different temperature sections according to the fact that the thermal stability of different components of the biomass is greatly different, so that the biomass-based BaO catalyst, deoxidized oil (12) and low-temperature flue gas (13) are obtained. The method specifically comprises the following steps:
(1) According to the fact that the thermal stability difference of different components of biomass is large, the crushed biomass is sent to a first-stage pressurized pyrolysis unit I to carry out pyrolysis at different temperature sections, and pyrolysis volatile matters (2), pyrolysis vapor (6) and pyrolysis coke (4) are obtained. The height of the biomass filling material is not more than 3/5 of the furnace body of the primary pressurized pyrolysis unit I. First, pyrolysis steam (6) was obtained by maintaining the flow rate of nitrogen at 100mL/min, the pressure at 0.5MPa, and the temperature at 200℃for 1.0 h. Then, the temperature was raised to 650℃and maintained for 1.5 hours, to obtain pyrolysis volatiles (2) and pyrolysis char (4).
(2) According to the fact that the thermal stability difference of different components of biomass is large, the crushed biomass is sent to a secondary pressurized pyrolysis unit II to carry out pyrolysis at different temperature sections. The height of the biomass is not more than 3/5 of the furnace body of the secondary pressurized pyrolysis unit. First, pyrolysis steam (6) was obtained by maintaining the flow rate of nitrogen at 100mL/min, the pressure at 0.5MPa, and the temperature at 200℃for 1.0 h. And (3) introducing pyrolysis steam (6) into an in-situ activation unit III, and in-situ activating pyrolysis coke (4) for 1.0h at the temperature of 650 ℃ and under the pressure of 0.5MPa to obtain high specific surface area activated carbon (7) and activated synthesis gas (8). The specific surface area of the activated carbon (7) with high specific surface area is 850m 2 /g。
(3) Raising the temperature of the secondary pressurized pyrolysis unit II to 650 ℃, and maintaining for 1.5h to obtain pyrolysis volatile components (3) and pyrolysis coke(5). The pyrolysis volatile component (3), the 10.0% BaO aerosol at 300 ℃ and the high specific surface area active carbon (7) enter a one-step activation, trapping and conversion deoxidization unit V at the same time, catalytic reforming reaction is carried out at 650 ℃ for 1.0h, the mass ratio of the high specific surface area active carbon to the pyrolysis volatile component (3) is 3.0, and the mass ratio of the active component aerosol to the high specific surface area active carbon is 0.10, so as to obtain the carbon-based BaO catalyst, the synthesis gas (11) and the deoxidized oil (12). The specific surface area of the carbon-based BaO catalyst (10) is 400m 2 The ash concentration per gram was 1.5wt.%, and the oxygen content of the deoxygenated oil (12) was 0.3%. CO in the synthesis gas (11) 2 Concentration of 5.0%, NO x Concentration of 0.06%, SO x The concentration was 0.09%, the hydrogen concentration was 15%, the methane concentration was 25%, and the CO concentration was 23%.
(4) The activated synthesis gas (8) and the synthesis gas (11) are introduced into an incineration unit VI, low-temperature flue gas (13) is obtained by incineration at 800 ℃, and heat energy generated by the incineration is supplied to a primary compression pyrolysis unit I and a secondary compression pyrolysis unit II. SO in the discharged low-temperature flue gas (13) 2 The discharge concentration was 10mg/m 3 ，NO x The discharge concentration was 25mg/m 3 。
The above embodiments are only described to assist in understanding the technical solution of the present invention and its core idea, and it should be noted that it will be obvious to those skilled in the art that several improvements and modifications can be made to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.
Claims (10)
1. A method for preparing deoxidized oil and carbon material with high specific surface area by using energy-saving biomass is characterized by comprising the following steps: according to the large difference of thermal stability of different components of biomass, biomass is subjected to step-by-step pressurized pyrolysis, activation, trapping conversion and incineration in sequence in different temperature sections to obtain a carbon-based catalyst (10), deoxidized oil (12) and low-temperature flue gas (13); the method specifically comprises the following steps: respectively feeding biomass (1) into a primary compression pyrolysis unit and a secondary compression pyrolysis unit to carry out compression pyrolysis at different temperature sections to obtain pyrolysis vapor (6), pyrolysis volatile matters (2)/(3) and pyrolysis coke (4)/(5); the pyrolysis steam (6) respectively carries out in-situ activation on the pyrolysis coke (4)/(5) through an in-situ activation unit to obtain activated carbon (7) with high specific surface area and activated synthesis gas (8); the high specific surface area activated carbon (7) enters a one-step activation, trapping, conversion and deoxidization unit and pyrolysis volatile matters (2)/(3) to perform catalytic reforming reaction in the atmosphere of active component aerosol (9) to obtain a carbon-based catalyst (10), synthesis gas (11) and deoxidized oil (12); the activated synthesis gas (8) and the synthesis gas (11) enter an incineration unit for incineration, and low-temperature flue gas (13) is obtained after energy is provided for a primary compression pyrolysis unit, a secondary compression pyrolysis unit and an in-situ activation unit, so that biomass low-energy consumption recycling is realized.
2. The method according to claim 1, characterized in that: pyrolysis vapor (6) obtained by the primary compression pyrolysis unit and the secondary compression pyrolysis unit is collected to the same container; the biomass is subjected to pressurized pyrolysis, in-situ activation and one-step activation, trapping, conversion and deoxidation to obtain deoxidized oil (12) and a carbon-based catalyst (10), and the deoxidized oil and the carbon-based catalyst are respectively collected into the same container.
3. The method according to claim 1, characterized in that: the biomass is subjected to primary/secondary pressurized pyrolysis unit, the flow rate of nitrogen is 100-200 mL/min, the pressure is 0.1-35 MPa, the temperature is 150-200 ℃ and is maintained for 0.5-1.0 h, pyrolysis vapor (6) is obtained, then the temperature is raised to 500-650 ℃ and is maintained for 0.8-1.5 h, and pyrolysis volatile components (2)/(3) and pyrolysis coke (4)/(5) are obtained.
4. A method according to any one of claims 1-3, characterized in that: the pyrolysis vapor (6) obtained by low-temperature pyrolysis of biomass enters an in-situ activation unit III/IV to obtain high-specific-surface-area activated carbon (7) and activated synthesis gas (8) by high temperature heat Jie Jiao (4)/(5), the activation pressure is 0.1-35 MPa, the activation temperature is 550-1000 ℃, the activation time is 0.5-1.0 h, and the mass ratio of the pyrolysis vapor (6) to the pyrolysis coke (4)/(5) is 0.1-0.8.
5. The method according to claim 4, wherein: the said sourceThe specific surface area of the activated carbon (7) with high specific surface area obtained by site activation is 100-1200 m 2 Ash concentration is 0.1-2.0 wt.%/g.
6. The method according to claim 1, characterized in that: the high specific surface area activated carbon (7) and biomass pyrolysis volatile components (2)/(3) are introduced into an activation trapping conversion deoxidizing unit in the atmosphere of an active component aerosol (9) to perform an activation catalytic reforming reaction, so that a carbon-based catalyst (10), synthesis gas (11) and deoxidized oil (12) are obtained, the reaction temperature is 550-900 ℃, the reaction pressure is 0.1-35 MPa, the reaction time is 0.5-2.0 h, the mass ratio of the pyrolysis volatile components (2)/(3) to the high specific surface area activated carbon (7) is 0.5-5.0, the mass concentration of the active components in the active component aerosol is 10-50%, and the mass ratio of the active component aerosol (9) to the high specific surface area activated carbon (7) is 0.01-0.20.
7. The method according to claim 6, wherein: the active component in the active component aerosol (9) is metal oxide comprising CaO and Fe 2 O 3 、MaO、K 2 O and BaO.
8. The method according to claim 6, wherein: the oxygen content of the deoxidized oil (12) obtained by the activated trapping, converting and deoxidizing is 0.1-1.0%, and the specific surface area of the carbon-based catalyst (10) obtained by the activated trapping, converting and deoxidizing is 100-1000 m 2 Ash concentration is 0.1-3.0 wt.%/g.
9. The method of claim 1, 4 or 6, wherein: the activated synthesis gas (8) obtained by in-situ activation and the synthesis gas (11) obtained by activation, trapping, conversion and deoxidation are burnt to obtain low-temperature flue gas (13), the energy is supplied to a pressurized pyrolysis unit and an in-situ activation unit, and the burning temperature is 700-1000 ℃.
10. The method according to claim 9, wherein: SO in low-temperature flue gas (13) x And NO x Is divided into discharge concentration of (2)Is not lower than 20mg/m 3 And 30mg/m 3 。
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