CN106947510A - The system and method that a kind of biomass graded sub-prime is utilized - Google Patents
The system and method that a kind of biomass graded sub-prime is utilized Download PDFInfo
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- CN106947510A CN106947510A CN201710299909.5A CN201710299909A CN106947510A CN 106947510 A CN106947510 A CN 106947510A CN 201710299909 A CN201710299909 A CN 201710299909A CN 106947510 A CN106947510 A CN 106947510A
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- 239000002028 Biomass Substances 0.000 title claims abstract description 112
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000007789 gas Substances 0.000 claims abstract description 172
- 238000000197 pyrolysis Methods 0.000 claims abstract description 155
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 94
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 57
- 239000001257 hydrogen Substances 0.000 claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000002309 gasification Methods 0.000 claims abstract description 52
- 239000000292 calcium oxide Substances 0.000 claims abstract description 47
- 235000012255 calcium oxide Nutrition 0.000 claims abstract description 46
- 239000003245 coal Substances 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 230000004913 activation Effects 0.000 claims abstract description 36
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 36
- 238000011069 regeneration method Methods 0.000 claims abstract description 30
- 230000008929 regeneration Effects 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 20
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011575 calcium Substances 0.000 claims abstract description 18
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000571 coke Substances 0.000 claims description 46
- 238000010521 absorption reaction Methods 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000004571 lime Substances 0.000 claims description 7
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 9
- 239000003818 cinder Substances 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 16
- 239000006096 absorbing agent Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000003463 adsorbent Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QLTZBYGZXPKHLF-UHFFFAOYSA-N 2-Propylsuccinic acid Chemical compound CCCC(C(O)=O)CC(O)=O QLTZBYGZXPKHLF-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
- C10K1/00—Purifying combustible gases containing carbon monoxide
- C10K1/20—Purifying combustible gases containing carbon monoxide by treating with solids; Regenerating spent purifying masses
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0913—Carbonaceous raw material
- C10J2300/093—Coal
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
- C10J2300/00—Details of gasification processes
- C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
- C10J2300/0953—Gasifying agents
- C10J2300/0966—Hydrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The present invention relates to the system and method that a kind of biomass graded sub-prime is utilized, the system includes biomass pyrolytic unit, Oil-gas Separation unit, PSA absorptive units, hydrogasification unit, regeneration unit and semicoke activation unit；Biomass pyrolytic unit includes biomass inlet, pyrolysis oil gas vent and biomass char outlet；Oil-gas Separation unit includes pyrolysis oil gas entrance, pyrolysis oil export and pyrolysis gas outlet；PSA absorptive units include pyrolysis gas entrance, hydrogen-rich gas outlet, quick lime entrance and the outlet of mixing calcium-based material；Hydrogasification unit includes coal nozzle, hydrogen-rich gas nozzle, the outlet of gasification cinder and oil gas vent；Regeneration unit includes mixing calcium-based material entrance, high temperature carbon dioxide outlet and quick lime outlet；Semicoke activation unit includes biomass char entrance, high temperature carbon dioxide entrance, activated carbon outlet.Biomass pyrolytic is prepared the techniques such as activated carbon with coal hydrogenation gasification and semicoke activation and coupled by the present invention, realizes the raising of system energy efficiency.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a system and a method for grading and separating utilization of biomass.
Background
Coal hydro-gasification refers to a process of reacting raw coal powder with a hydrogen-containing reaction gas at high temperature and high pressure (800-1000 ℃, 3-8 MPa) to generate a methane-rich gas and a light oil product. Compared with the traditional coal gasification, the coal hydro-gasification has the characteristics of simple process, high thermal efficiency and low pollution, but the price of hydrogen is high, so that the search for the alternative atmosphere of hydrogen becomes the attention of many researchers. The biomass is a renewable energy source, the net increase yield is huge, the wastes of agriculture, forestry and animal husbandry are generally directly used as fuel to burn at present, but the problems of insufficient burning and serious environmental pollution are often caused, compared with coal, the biomass has high volatile matter content, a large amount of light tar and pyrolysis gas can be obtained by pyrolysis, and the pyrolysis gas contains high content of hydrogen, carbon monoxide and methane and can be used as a hydrogen source for coal hydro-gasification; meanwhile, the pyrolyzed biomass coke has the advantages of high activity, low sulfur nitrogen and ash content and large specific surface area, and is suitable to be used as a raw material for preparing activated carbon, so that the pyrolyzed biomass coke is widely concerned and applied. Therefore, the prior art cannot utilize pyrolysis gas and semicoke generated by biomass pyrolysis in a grading and quality-separating manner and couple coal hydro-gasification and activated carbon preparation to improve the comprehensive utilization efficiency.
Disclosure of Invention
In order to solve the technical problems, the invention aims to organically couple the processes of preparing the activated carbon by biomass pyrolysis, powdered coal hydro-gasification and semicoke activation and the like, and carry out graded and quality-divided utilization on pyrolysis gas and semicoke generated by biomass pyrolysis so as to improve the energy efficiency of a system.
In order to achieve the purpose, the invention provides a system for biomass graded and quality-divided utilization, which comprises a biomass pyrolysis unit, an oil-gas separation unit, a PSA (pressure swing adsorption) unit, a hydro-gasification unit, a regeneration unit and a semicoke activation unit; wherein,
the biomass pyrolysis unit comprises a biomass inlet, a pyrolysis oil gas outlet and a biomass coke outlet;
the oil-gas separation unit comprises a pyrolysis oil-gas inlet, a pyrolysis oil outlet and a pyrolysis gas outlet, and the pyrolysis oil-gas inlet is connected with the pyrolysis oil-gas outlet;
the PSA absorption unit comprises a pyrolysis gas inlet, a hydrogen-rich gas outlet, a quicklime inlet and a mixed calcium-based material outlet, and the pyrolysis gas inlet is connected with the pyrolysis gas outlet;
the PSA absorption unit comprises a gas distributor arranged at the bottom, and a massive quicklime bed layer and a solid filter bed layer which are distributed from bottom to top;
the hydro-gasification unit comprises a coal powder nozzle, a hydrogen-rich gas nozzle, a gasification coke residue outlet and an oil gas outlet, and the hydrogen-rich gas nozzle is connected with the hydrogen-rich gas outlet;
the regeneration unit comprises a mixed calcium-based material inlet, a high-temperature carbon dioxide outlet and a quick lime outlet, the mixed calcium-based material inlet is connected with the mixed calcium-based material outlet, and the quick lime outlet is connected with the quick lime inlet;
the semicoke activation unit comprises a biomass coke inlet, a high-temperature carbon dioxide inlet, an activated carbon outlet and a carbon dioxide outlet, wherein the biomass coke inlet is connected with the biomass coke outlet, and the high-temperature carbon dioxide inlet is connected with the high-temperature carbon dioxide outlet.
Further, the biomass pyrolysis unit is a heat-carrier-free heat accumulating type preheating furnace.
The heat-carrier-free heat accumulating type preheating furnace is characterized in that double-layer heat accumulating type radiant tubes are arranged in the heat accumulating type preheating furnace, any layer of heat accumulating type radiant tubes are uniformly distributed in the horizontal direction of the preheating furnace, and the double-layer heat accumulating type radiant tubes are distributed up and down in the vertical direction of the preheating furnace.
In particular, the apparatus used in the PSA absorption unit is a pressurized PSA absorber.
The device used by the hydro-gasification unit is a gasification furnace.
The device used by the regeneration unit is a high-temperature calcination device.
The device used by the semicoke activation unit is an activation chamber.
Preferably, the hydrogen-rich gas nozzles in the hydro-gasification unit are even in number and are symmetrically arranged around the pulverized coal nozzle.
Further, the system also comprises a spiral discharging machine, wherein the spiral discharging machine is arranged inside the biomass coke outlet of the biomass pyrolysis unit.
The invention also provides a method for grading and separating the biomass for utilization, which is characterized by comprising the following steps:
A. pyrolysis: feeding biomass into the biomass pyrolysis unit for pyrolysis to obtain pyrolysis oil gas and biomass coke;
B. oil-gas separation: separating the pyrolysis oil gas into pyrolysis oil and pyrolysis gas in the oil-gas separation unit;
PSA absorption: treating the pyrolysis gas in the PSA absorption unit to obtain hydrogen-rich gas;
D. hydro-gasification: inputting the hydrogen-rich gas serving as a hydrogen source into the hydro-gasification unit to perform hydro-gasification reaction with the pulverized coal;
E. and (3) quicklime regeneration: conveying the calcined lime bed layer of the PSA absorption unit after saturated adsorption to the regeneration unit for calcination to generate calcined lime and high-temperature carbon dioxide; wherein the raw lime is sent to the PSA absorption unit for recycling;
F. activation of semicoke: conveying the high-temperature carbon dioxide generated by the regeneration unit to the activation unit to activate the biomass coke generated by pyrolysis.
Specifically, in the step A, the biomass is primarily crushed before pyrolysis, and the length is controlled to be less than or equal to 10 mm.
More specifically, in the step A, the pyrolysis temperature of the biomass pyrolysis unit is controlled at 650 ℃, and the pyrolysis time is 30-60 min.
And further, in the step C, under the action of a gas distributor, the pyrolysis gas is uniformly distributed in the PSA absorption unit and is sequentially adsorbed by a blocky quicklime bed layer and a solid filter bed layer to obtain the hydrogen-rich gas.
Preferably, the pressure in the PSA absorption unit is controlled to be in the range of 0.4 to 1.0 MPa.
Further, in the step D, the reaction temperature of the hydro-gasification unit is controlled to be 800-.
Specifically, in the step E, the regeneration temperature is controlled at 900-.
Specifically, in the step F, the activation temperature is controlled at 850-950 ℃.
The technical scheme adopted by the invention has the following advantages:
(1) the method is characterized in that agricultural, forestry and animal husbandry wastes are used as raw materials, a hydrogen source of coal hydro-gasification reaction is obtained through a pyrolysis technology, and high-performance activated carbon is generated through self activation, so that waste is changed into valuable;
(2) the biomass is pyrolyzed by adopting a heat-carrier-free heat accumulating type preheating furnace, so that the heat utilization rate can be improved, and the quality of pyrolysis gas can be improved; pyrolysis gas generated by biomass pyrolysis is purified and dedusted and then used as a hydrogen source for coal hydro-gasification reaction, so that the cost of the coal hydro-gasification hydrogen source is reduced;
(3) in the process of obtaining hydrogen-rich gas by PSA absorption technology with CaO as absorbent, the CaO bed layer fully absorbs CO in the pyrolysis gas2After being mixed with water, the mixed gas can be recycled after being calcined in the regeneration unit, and simultaneously, high-temperature CO required by the activation unit is generated2；
(4) Pyrolysis produced biomass char and high temperature CO produced by a regeneration unit2Can directly enter an activation chamber at high temperature to be activated to obtain the activated carbon, can fully utilize the sensible heat of gas and solid, and improve the energy utilization rate of the whole system.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a schematic view of a system for fractional and separate utilization of biomass according to the present invention;
1-biomass pyrolysis unit, 2-PSA absorption unit, 3-hydro-gasification unit, 4-regeneration unit and 5-semicoke activation unit;
11-biomass inlet, 12-pyrolysis oil gas outlet, 13-pyrolysis oil outlet, 14-pyrolysis gas outlet and 15-biomass coke outlet;
21-pyrolysis gas inlet, 22-gas distributor, 23-blocky quicklime bed layer, 24-solid filter bed layer, 25-hydrogen-rich gas outlet, 26-quicklime inlet and 27-mixed calcium-based material outlet;
31-a coal powder nozzle, 32-a hydrogen-rich gas nozzle, 33-an oil gas outlet and 34-a gasified coke residue outlet;
41-a mixed calcium-based material inlet, 42-a high-temperature carbon dioxide outlet and 43-a quicklime outlet;
51-biomass coke inlet, 52-high temperature carbon dioxide inlet, 53-activated carbon outlet and 54-carbon dioxide outlet.
FIG. 2 is a process flow diagram of the present invention for the fractionation and quality-grading of biomass.
Detailed Description
The following detailed description of the present invention, taken in conjunction with the accompanying drawings and examples, is provided to enable the invention and its various aspects and advantages to be better understood. However, the specific embodiments and examples described below are for illustrative purposes only and are not limiting of the invention.
In order to realize the graded and quality-divided utilization of biomass and coal, the invention organically couples the processes of preparing activated carbon by biomass pyrolysis, pulverized coal hydro-gasification and semicoke activation, and the like, and provides a system for graded and quality-divided utilization of biomass, as shown in fig. 1, the system comprises a biomass pyrolysis unit 1, an oil-gas separation unit (not shown), a PSA absorption unit 2, a hydro-gasification unit 3, a regeneration unit 4 and a semicoke activation unit 5; wherein,
the biomass pyrolysis unit 1 comprises a biomass inlet 11, a pyrolysis oil gas outlet 12 and a biomass coke outlet 15;
an oil-gas separation unit is arranged outside the pyrolysis oil-gas outlet 12 to separate pyrolysis oil gas into pyrolysis oil and pyrolysis gas; the oil-gas separation unit comprises a pyrolysis oil-gas inlet, a pyrolysis oil outlet 13 and a pyrolysis gas outlet 14, the pyrolysis oil outlet 13 is used for collecting pyrolysis oil, the pyrolysis gas is output from the outlet 14 and then enters the PSA absorption unit 2 through a pipeline, and the pyrolysis oil-gas inlet is connected with the pyrolysis oil-gas outlet;
the PSA absorption unit 2 comprises a pyrolysis gas inlet 21, a hydrogen-rich gas outlet 25, a quick lime inlet 26 and a mixed calcium-based material outlet 27, wherein the pyrolysis gas inlet 21 is connected with the pyrolysis gas outlet 14 of an oil-gas separation unit externally arranged on the biomass pyrolysis unit 1;
the PSA absorption unit 2 comprises a gas distributor 22 arranged at the bottom, and a massive quicklime bed layer 23 and a solid filter bed layer 24 which are distributed from bottom to top, wherein the quicklime bed layer can adsorb water and carbon dioxide in the pyrolysis gas to obtain a mixed calcium-based material, and the solid filter bed layer can remove solid dust and other impurities carried by the gas to obtain a hydrogen-rich gas;
the hydro-gasification unit 3 comprises a coal powder nozzle 31, a hydrogen-rich gas nozzle 32, an oil gas outlet 33 and a gasification coke residue outlet 34, wherein the hydrogen-rich gas nozzle 32 is connected with the hydrogen-rich gas outlet 25;
the regeneration unit 4 comprises a mixed calcium-based material inlet 41, a high-temperature carbon dioxide outlet 42 and a quick lime outlet 43, wherein the mixed calcium-based material inlet 41 is connected with the mixed calcium-based material outlet 27, and the quick lime outlet 43 is connected with the quick lime inlet 26;
the semicoke activation unit 5 comprises a biomass coke inlet 51, a high-temperature carbon dioxide inlet 52, an activated carbon outlet 53 and a carbon dioxide outlet 54, wherein the biomass coke inlet 51 is connected with the biomass coke outlet 15, and the high-temperature carbon dioxide inlet 52 is connected with the high-temperature carbon dioxide outlet 42.
Further, the biomass pyrolysis unit 1 is a heat accumulating type preheating furnace without heat carriers. The heat-carrier-free heat accumulating type preheating furnace is characterized in that double-layer heat accumulating type radiant tubes are arranged in the heat accumulating type preheating furnace, any layer of heat accumulating type radiant tubes are uniformly distributed in the horizontal direction of the preheating furnace, and the double-layer heat accumulating type radiant tubes are distributed up and down in the vertical direction of the preheating furnace.
In particular, the apparatus used by the PSA absorption unit 2 is a pressurized PSA absorber. The apparatus used in the hydro-gasification unit 3 is a gasification furnace. The apparatus used in the regeneration unit 4 is a high-temperature calcination apparatus. The device used by the semicoke activation unit 5 is an activation chamber.
Preferably, the hydrogen-rich gas nozzles in the hydro-gasification unit 3 are even in number and symmetrically arranged around the pulverized coal nozzles, so that the hydrogen-rich gas and the pulverized coal can be fully mixed.
Further, the system further comprises a spiral discharging machine (not shown in the figure), and the spiral discharging machine is arranged inside the biomass coke outlet of the pyrolysis device and is used for processing the biomass coke to obtain powdery substances.
The invention also provides a method for carrying out grading and quality-grading utilization on biomass, and the process is shown in figure 2, and the method comprises the following steps:
A. pyrolysis: feeding biomass into the biomass pyrolysis unit for pyrolysis to obtain pyrolysis oil gas and biomass coke; wherein, the biomass can be dried before pyrolysis; the biomass comprises one or more of agricultural, forestry and animal husbandry wastes;
B. oil-gas separation: separating the pyrolysis oil gas into pyrolysis oil and pyrolysis gas in the oil-gas separation unit;
PSA absorption: the separated pyrolysis gas enters the PSA absorption unitFirstly, under the action of gas distributor, the gas is uniformly distributed in the pressurized PSA absorber, and passes through blocky quicklime bed layer and solid filter bed layer in turn to adsorb water and CO in the pyrolysis gas2And part of other impurities to obtain hydrogen-rich gas;
wherein, the main components of the separated pyrolysis gas are hydrogen (18-30%), methane (20-30%), carbon monoxide (15-25%), carbon dioxide (20-30%) and water (10-20%);
the main components of the hydrogen-rich gas are hydrogen (30-50%), methane (30-50%) and carbon monoxide (25-40%).
D. Hydro-gasification: taking the hydrogen-rich gas as a hydrogen source, entering the hydro-gasification unit through a nozzle, and carrying out hydro-gasification reaction with the pulverized coal to obtain methane-rich gas and light tar;
E. and (3) quicklime regeneration: conveying the saturated quicklime bed layer of the PSA absorption unit, namely the mixed calcium-based material, to the regeneration unit for calcination to regenerate quicklime and high-temperature carbon dioxide; wherein the raw lime is sent to the PSA absorption unit for recycling;
F. activation of semicoke: and conveying the high-temperature carbon dioxide generated by the regeneration unit to the activation unit, and activating the biomass coke generated by pyrolysis as an activating agent to obtain the activated carbon with developed micropores and high specific surface area, thereby realizing the purpose of resource utilization of gas-solid waste.
Specifically, in the step A, the biomass is primarily crushed before pyrolysis, and the length is controlled to be less than or equal to 10 mm.
More specifically, in the step A, the pyrolysis temperature of the biomass pyrolysis unit is controlled at 650 ℃, and the pyrolysis time is 30-60 min.
And further, in the step C, under the action of a gas distributor, the pyrolysis gas is uniformly distributed in the PSA absorption unit and is sequentially adsorbed by a blocky quicklime bed layer and a solid filter bed layer to obtain the hydrogen-rich gas.
Preferably, the pressure in the PSA absorption unit is controlled to be in the range of 0.4 to 1.0 MPa.
Further, in the step D, the reaction temperature of the hydro-gasification unit is controlled to be 800-.
Specifically, in the step E, the regeneration temperature is controlled at 900-.
Specifically, in the step F, the activation temperature is controlled at 850-950 ℃.
The process of the present invention for fractionation and quality-separation of biomass will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
And (3) feeding the biomass with the length of less than 10mm into a heat-carrier-free regenerative preheating furnace. Biomass is pyrolyzed in a preheating furnace to generate biomass coke and pyrolysis oil gas, the pyrolysis temperature is 600 ℃, and the pyrolysis time is 30 min; obtaining light pyrolysis oil and pyrolysis gas after the pyrolysis oil gas is subjected to oil-gas separation; adding the biomass coke into an activation chamber through closed heat-preservation conveying equipment; directly collecting the light pyrolysis oil, purifying and storing; the pyrolysis gas is conveyed to a PSA absorber through a pipeline, passes through a quicklime bed layer under 0.6Mpa, and removes moisture and CO in the pyrolysis gas2And the gas is dedusted and purified by a solid filter bed to obtain hydrogen-rich gas; hydrogen-rich gas enters the hydrogenation gasification furnace through a nozzle, is fully mixed with coal powder sprayed by a coal powder nozzle, and is subjected to hydrogenation gasification reaction at 850 ℃ and 2.0MPa to obtain methane-rich gas, light tar and gasified coke slag; conveying the adsorbed quicklime bed layer to a regeneration unit, and calcining at 900 ℃ to obtain high-temperature carbon dioxide and quicklime; the quicklime can be taken as an adsorbent and conveyed to the PSA adsorption unit again; high temperature carbon dioxide is delivered directly to the activation chamber at 85Activating the biomass coke at 0 ℃ to obtain the high-performance activated carbon.
Example 2
The biomass grading and quality-grading utilization process of the embodiment has the same steps as those of the embodiment 1, but the process parameters are different, and specifically, the process comprises the following steps:
and (3) feeding the biomass with the length of less than 10mm into a heat-carrier-free regenerative preheating furnace. Biomass is pyrolyzed in a preheating furnace to generate biomass coke and pyrolysis oil gas, wherein the pyrolysis temperature is 500 ℃, and the pyrolysis time is 60 min; obtaining light pyrolysis oil and pyrolysis gas after the pyrolysis oil gas is subjected to oil-gas separation; adding the biomass coke into an activation chamber through closed heat-preservation conveying equipment; directly collecting the light pyrolysis oil, purifying and storing; the pyrolysis gas is conveyed to a PSA absorber through a pipeline, passes through a quicklime bed layer under 0.8Mpa, and removes moisture and CO in the pyrolysis gas2And the gas is dedusted and purified by a solid filter bed to obtain hydrogen-rich gas; hydrogen-rich gas enters the hydrogenation gasification furnace through a nozzle, is fully mixed with coal powder sprayed by a coal powder nozzle, and is subjected to hydrogenation gasification reaction at 800 ℃ and 2.0MPa to obtain methane-rich gas, light tar and gasified coke slag; conveying the adsorbed quicklime bed layer to a regeneration unit, and calcining at 1000 ℃ to obtain high-temperature carbon dioxide and quicklime; the quicklime can be taken as an adsorbent and conveyed to the PSA adsorption unit again; high-temperature carbon dioxide is directly conveyed to an activation chamber, and the biomass coke is activated at 950 ℃ to obtain high-performance activated carbon.
Example 3
The process for implementing biomass grading and quality-grading utilization is the same as the step of the embodiment 1, but the process parameters are different, and specifically the following steps are adopted:
and (3) feeding the biomass with the length of less than 10mm into a heat-carrier-free regenerative preheating furnace. Pyrolyzing biomass in a preheating furnace to generate biomass coke and pyrolysis oil gas, wherein the pyrolysis temperature is 650 ℃, and the pyrolysis time is 50 min; obtaining light weight after pyrolysis oil gas is subjected to oil-gas separationPyrolysis oil and pyrolysis gas; adding the biomass coke into an activation chamber through closed heat-preservation conveying equipment; directly collecting the light pyrolysis oil, purifying and storing; the pyrolysis gas is conveyed to a PSA absorber through a pipeline, passes through a quicklime bed layer under the pressure of 1Mpa, and is used for removing moisture and CO in the pyrolysis gas2And the gas is dedusted and purified by a solid filter bed to obtain hydrogen-rich gas; hydrogen-rich gas enters the hydrogenation gasification furnace through a nozzle, is fully mixed with coal powder sprayed by a coal powder nozzle, and is subjected to hydrogenation gasification reaction at 900 ℃ and 3.0MPa to obtain methane-rich gas, light tar and gasified coke slag; conveying the adsorbed quicklime bed layer to a regeneration unit, and calcining at 900 ℃ to obtain high-temperature carbon dioxide and quicklime; the quicklime can be taken as an adsorbent and conveyed to the PSA adsorption unit again; and directly conveying the high-temperature carbon dioxide to an activation chamber, and activating the biomass coke at 900 ℃ to obtain the high-performance activated carbon.
Example 4
The process for implementing biomass grading and quality-grading utilization is the same as the step of the embodiment 1, but the process parameters are different, and specifically the following steps are adopted:
and (3) feeding the biomass with the length of less than 10mm into a heat-carrier-free regenerative preheating furnace. Pyrolyzing biomass in a preheating furnace to generate biomass coke and pyrolysis oil gas, wherein the pyrolysis temperature is 600 ℃, and the pyrolysis time is 40 min; obtaining light pyrolysis oil and pyrolysis gas after the pyrolysis oil gas is subjected to oil-gas separation; adding the biomass coke into an activation chamber through closed heat-preservation conveying equipment; directly collecting the light pyrolysis oil, purifying and storing; the pyrolysis gas is conveyed to a PSA absorber through a pipeline, passes through a quicklime bed layer under 0.4Mpa, and removes moisture and CO in the pyrolysis gas2And the gas is dedusted and purified by a solid filter bed to obtain hydrogen-rich gas; hydrogen-rich gas enters the hydrogenation gasification furnace through a nozzle, is fully mixed with coal powder sprayed by a coal powder nozzle, and is subjected to hydrogenation gasification reaction at 1000 ℃ and 1.0MPa to obtain methane-rich gas, light tar and gasified coke slag; conveying the adsorbed quicklime bed layer to a regeneration unit, and calcining at 1000 ℃ to obtain high-temperature carbon dioxide and quicklime; the quicklime can be used as adsorptionRe-delivering the agent to the PSA adsorption unit; and directly conveying the high-temperature carbon dioxide to an activation chamber, and activating the biomass coke at 900 ℃ to obtain the high-performance activated carbon.
In the embodiment, the agricultural, forestry and animal husbandry waste is used as the pyrolysis raw material, so that the hydrogen source of coal hydro-gasification and the activated carbon prepared by self activation can be obtained while biomass resources are fully utilized, and waste is changed into valuable; meanwhile, the biomass pyrolysis is finished in a heat accumulating type preheating furnace without heat carrier, the obtained pyrolysis gas has high quality, and H is absorbed by PSA2、CH4The CO content is high, the hydrogen source cost of pulverized coal gasification can be reduced by taking the CO as a hydrogen source of coal hydro-gasification, and high-calorific-value gas is finally obtained; in addition, biomass char produced from biomass pyrolysis and CO produced by the regeneration unit2The sensible heat of gas and solid can be fully utilized, thereby reducing the energy consumption of the whole system.
Finally, it should be noted that: it should be understood that the above examples are only for clearly illustrating the present invention and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. A system for biomass grading and quality-based utilization comprises a biomass pyrolysis unit, an oil-gas separation unit, a PSA absorption unit, a hydro-gasification unit, a regeneration unit and a semicoke activation unit; wherein,
the biomass pyrolysis unit comprises a biomass inlet, a pyrolysis oil gas outlet and a biomass coke outlet;
the oil-gas separation unit comprises a pyrolysis oil-gas inlet, a pyrolysis oil outlet and a pyrolysis gas outlet, and the pyrolysis oil-gas inlet is connected with the pyrolysis oil-gas outlet;
the PSA absorption unit comprises a pyrolysis gas inlet, a hydrogen-rich gas outlet, a quicklime inlet and a mixed calcium-based material outlet, and the pyrolysis gas inlet is connected with the pyrolysis gas outlet;
the PSA absorption unit comprises a gas distributor arranged at the bottom, and a massive quicklime bed layer and a solid filter bed layer which are distributed from bottom to top;
the hydro-gasification unit comprises a coal powder nozzle, a hydrogen-rich gas nozzle, a gasification coke residue outlet and an oil gas outlet, and the hydrogen-rich gas nozzle is connected with the hydrogen-rich gas outlet;
the regeneration unit comprises a mixed calcium-based material inlet, a high-temperature carbon dioxide outlet and a quick lime outlet, the mixed calcium-based material inlet is connected with the mixed calcium-based material outlet, and the quick lime outlet is connected with the quick lime inlet;
the semicoke activation unit comprises a biomass coke inlet, a high-temperature carbon dioxide inlet, an activated carbon outlet and a carbon dioxide outlet, wherein the biomass coke inlet is connected with the biomass coke outlet, and the high-temperature carbon dioxide inlet is connected with the high-temperature carbon dioxide outlet.
2. The system of claim 1,
the biomass pyrolysis unit is a heat-carrier-free heat accumulating type preheating furnace; the heat-carrier-free heat accumulating type preheating furnace is characterized in that double-layer heat accumulating type radiant tubes are arranged in the heat accumulating type preheating furnace, any layer of heat accumulating type radiant tubes are uniformly distributed in the horizontal direction of the preheating furnace, and the double-layer heat accumulating type radiant tubes are distributed up and down in the vertical direction of the preheating furnace.
3. The system of claim 1,
the number of the hydrogen-rich gas nozzles in the hydro-gasification unit is even, and the hydrogen-rich gas nozzles are symmetrically arranged around the pulverized coal nozzles.
4. The system of claim 1,
the system further comprises a spiral discharging machine, wherein the spiral discharging machine is arranged inside the biomass coke outlet of the biomass pyrolysis unit.
5. A method for the fractionated use of biomass using the system of any one of claims 1 to 4 including the steps of:
A. pyrolysis: feeding biomass into the biomass pyrolysis unit for pyrolysis to obtain pyrolysis oil gas and biomass coke;
B. oil-gas separation: separating the pyrolysis oil gas into pyrolysis oil and pyrolysis gas in the oil-gas separation unit;
PSA absorption: treating the pyrolysis gas in the PSA absorption unit to obtain hydrogen-rich gas;
D. hydro-gasification: inputting the hydrogen-rich gas serving as a hydrogen source into the hydro-gasification unit to perform hydro-gasification reaction with the pulverized coal;
E. and (3) quicklime regeneration: conveying the calcined lime bed layer of the PSA absorption unit after saturated adsorption to the regeneration unit for calcination to generate calcined lime and high-temperature carbon dioxide; wherein the raw lime is sent to the PSA absorption unit for recycling;
F. activation of semicoke: conveying the high-temperature carbon dioxide generated by the regeneration unit to the activation unit to activate the biomass coke generated by pyrolysis.
6. The method according to claim 5, wherein in the step A, the biomass is primarily crushed before pyrolysis, and the length is controlled to be less than or equal to 10 mm.
7. The method according to claim 5, wherein, in the step C,
and under the action of a gas distributor, uniformly distributing the pyrolysis gas in the PSA absorption unit, and sequentially adsorbing the pyrolysis gas by a blocky quicklime bed layer and a solid filter bed layer to obtain the hydrogen-rich gas.
8. The method as claimed in claim 7, wherein the pressure in the PSA absorption unit is controlled to be 0.4-1.0 Mpa.
9. The method according to claim 5, wherein in step D,
controlling the reaction temperature of the hydro-gasification unit at 800-.
10. The method as claimed in claim 5, wherein the regeneration temperature is controlled at 900-1000 ℃ in step E.
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