CN107699306B - Quality-improving denitrification modification method for utilizing high-nitrogen biomass waste as fuel - Google Patents

Quality-improving denitrification modification method for utilizing high-nitrogen biomass waste as fuel Download PDF

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CN107699306B
CN107699306B CN201711037641.4A CN201711037641A CN107699306B CN 107699306 B CN107699306 B CN 107699306B CN 201711037641 A CN201711037641 A CN 201711037641A CN 107699306 B CN107699306 B CN 107699306B
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fuel
unit
flue gas
baking
drying
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CN107699306A (en
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吴创之
詹昊
庄修政
阴秀丽
袁洪友
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Guangzhou Institute of Energy Conversion of CAS
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Guangzhou Institute of Energy Conversion of CAS
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    • 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
    • C10L5/00—Solid fuels
    • C10L5/40—Solid fuels essentially based on materials of non-mineral origin
    • 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
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C10L9/083—Torrefaction
    • 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
    • C10L9/00—Treating solid fuels to improve their combustion
    • C10L9/08—Treating solid fuels to improve their combustion by heat treatments, e.g. calcining
    • C10L9/086—Hydrothermal carbonization
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Solid Fuels And Fuel-Associated Substances (AREA)

Abstract

The invention provides a quality-improving denitrification modification method for utilizing high-nitrogen biomass waste as fuel, which comprises a hydrothermal treatment unit, a dehydration unit, a drying unit, a baking unit, a heat supply unit, a flue gas distribution unit, a slurry treatment unit for balancing materials and a water storage device, wherein the hydrothermal treatment unit, the dehydration unit, the drying unit and the baking unit are used for modifying the high-nitrogen biomass waste in sequence. The method has the advantages that the dry-based heat value of the modified fuel obtained by the method is increased by 12-34%, the nitrogen removal rate of the fuel is 55-75%, the moisture content is lower than 5%, the high-efficiency clean thermochemical utilization of the rear end of the modified fuel can be realized, the coupling process is simple, the operability is high, no pollution is caused, the energy consumption and the energy loss are small, and the pretreatment method can effectively improve the recycling value of the high-nitrogen biomass waste.

Description

Quality-improving denitrification modification method for utilizing high-nitrogen biomass waste as fuel
The technical field is as follows:
the invention belongs to the technical field of biomass resource utilization, and particularly relates to a quality-improving denitrification modification method for utilizing high-nitrogen biomass waste as fuel.
Background art:
in the agricultural, forestry and industrial fields, the residues, by-products or wastes generated in the processes related to processing, production and utilization of biomass can be collectively called as biomass wastes. The biomass wastes account for a great proportion of biomass resources in China, the yield is huge, and according to statistical data, the annual yield of the current agricultural, forestry and industrial biomass wastes respectively exceeds 9 hundred million tons, 2 hundred million tons and 4 hundred million tons. The biomass wastes are converted into high-value-added bio-based products by adopting a thermochemical (pyrolysis, gasification or combustion) means or serve the industrial and civil heating fields, and the biomass wastes are typical forms of high-efficiency resource utilization, and can relieve the pressure brought by the shortage of traditional fossil energy and environmental pollution at present.
However, these wastes derived as biomass inevitably bring harmful and useless components such as moisture, ash and nitrogen components, etc. during the formation and source thereof, not only reducing the energy grade thereof, but also increasing the technical difficulty and economic cost for utilizing it as fuel. Particularly, as the biomass wastes relate to a complex process, harmful and useless components in the biomass wastes, such as sewage sludge, antibiotic fungi residues and peat, have very similar physicochemical properties. On one hand, high water content is one of typical characteristics, effective dehydration is the primary step of fuel utilization, and due to the large amount of hydrophilic functional groups, the wrapping of water molecules by organic polymers, the van der waals force between bonds and the like, the existing water molecules have high stability, the traditional mechanical dehydration and thermal drying dehydration have large limitation, the mechanical dehydration efficiency is low, the thermal drying dehydration energy consumption is high, and a low-energy-consumption and high-efficiency dehydration method is very necessary for fuel utilization. On the other hand, a high nitrogen content is another characteristic feature due to intrinsic growth itself or external addition. In the heat utilization process of biomass, the temperature of reaction is not too high, and NO is generatedxNO produced by heat utilization of biomass, essentially from fuel type (direct or indirect conversion of fuel nitrogen)xNot only can cause environmental problems such as acid rain, greenhouse effect, photochemical smog, ozone layer damage and the like, but also is the PM in the atmosphere2.5Is a significant source of. With environmental protection to NOxThe control and emission requirements are increasingly strict, and the high nitrogen content becomes a key factor for restricting the clean utilization of the biomass waste as fuel. Furthermore, due to the source and origin, the presence of fuel nitrogen in these wastes, in addition to relatively stable protein nitrogen, also presents considerable labile nitrogen functionality, which makes it possible to effectively remove fuel nitrogen prior to thermal utilization using suitable pretreatment methods.
In addition, the biomass wastes have wide sources and huge yield, and are increased year by year, according to data statistics of 2009, the biomass wastes respectively reach 1700 (sewage sludge), 1200 (antibiotic bacterial residues) and 200 (peat) ten thousand tons per year, and the main problems to be solved urgently as fuel utilization are basically the same due to the similar physicochemical properties of fuels, so that a universal quality-improving and denitrification-coupling pretreatment process or method is sought, the effective reuse value of the process is improved, and the method has very important significance.
The invention content is as follows:
the invention aims to provide a pretreatment method for quality-improving, denitrification and modification of high-nitrogen biomass waste, so as to reduce harmful and useless components in the high-nitrogen biomass waste, improve the energy quality of the high-nitrogen biomass waste and realize better utilization of the high-nitrogen biomass waste as fuel.
The invention aims to provide an upgrading denitrification modification method for utilizing high-nitrogen biomass waste as fuel, which comprises the following steps:
(1) under the thermal action of hydrothermal flue gas, after high-nitrogen biomass waste and water enter a hydrothermal treatment unit to be mixed, carrying out hydrothermal preliminary quality improvement and denitrification treatment to obtain preliminary modified slurry, wherein the temperature of the hydrothermal treatment unit is controlled to be 180-210 ℃, the hydrothermal treatment time is 10-60 min, the fuel nitrogen of the preliminary modified slurry is reduced by 40-55%, and the unit dry basis heat value is improved by 2-7%;
(2) conveying the primary modified slurry obtained in the step (1) to a dehydration unit for dehydration treatment to obtain slurry and primary modified wet fuel, wherein the dehydration treatment time is 15-25 min, the slurry is conveyed to a slurry treatment unit to obtain treatment liquid and precipitates, and the treatment liquid is returned to the hydrothermal treatment unit in the step (1) to form recycling; the dehydration unit realizes dehydration by adopting a centrifugal dehydration mode or a mechanical filter pressing mode, and when the dehydration is carried out by adopting the centrifugal dehydration mode, the rotating speed is 1000-2500 rpm, and the moisture content of the preliminary modified wet fuel is 50-60%;
(3) conveying the primary modified wet fuel obtained in the step (2) to a drying unit, and drying under the thermal action of dry flue gas to obtain primary modified dry fuel with the water content of less than 13%, wherein the temperature of the drying unit is controlled to be 85-110 ℃, and the drying time is 20-30 min;
(4) and (4) conveying the primary modified dry fuel obtained in the step (3) to a baking unit, and under the thermal action of baking flue gas, further performing quality improvement and denitrification treatment on the primary modified dry fuel, wherein the temperature of the baking unit is controlled to be 250-300 ℃, and the baking treatment time is 5-10 min, so as to obtain baking gas and a product modified dry fuel. The water content of the modified dry fuel of the product obtained by the baking unit process is lower than 5 percent, the nitrogen of the fuel is reduced by 25 to 40 percent, and the unit dry basis heat value is improved by 10 to 25 percent.
Aiming at the characteristic that the high-nitrogen biomass waste contains considerable unstable nitrogen functional groups (inorganic nitrogen and easily decomposed protein nitrogen), the invention adopts the sequential working procedures of hydrothermal treatment and baking to decompose the contained unstable nitrogen and transfer the nitrogen to liquid phase or gas phase, thereby realizing the effective removal of solid phase fuel nitrogen in two steps, and regarding the fuel nitrogen removal rate, the nitrogen removal rate of a hydrothermal treatment unit is 40-55 percent, and the nitrogen removal rate of a baking unit is 25-40 percent, thereby effectively reducing the nitrogen from the fuel to pollutant NO of the high-nitrogen biomass waste in the rear-end fuel utilization process from the rootxThe transformation of (3).
Meanwhile, in the processes of hydrothermal treatment and baking, organic functional groups with weak bond energy are easy to decompose firstly, such as dehydroxylation, decarboxylation and other reactions, so that the proportion of organic elements in the fuel is changed, the carbon and hydrogen contents are obviously increased, and the oxygen content is reduced, therefore, the heat value of the dry-based fuel is increased to a certain extent in both processes, the energy density of the fuel is improved, for example, the dry-based heat value of unit fuel is increased by 2-7% by a hydrothermal treatment unit, and the baking unit is increased by 10-25%.
The invention realizes effective quality improvement (dehydration and energy density improvement) and denitrification of high-nitrogen biomass waste under the condition of basic self-heating and no pollution through a reasonable coupling pretreatment process, the method integrates the fuel nitrogen removal rate of about 55-75 percent, the fuel dry-based heat value is increased by about 12-34 percent, the obtained modified dry fuel has large energy density, low nitrogen content and low moisture, and the high-efficiency clean thermochemical utilization of the rear end of the modified dry fuel can be realized.
Preferably, one part of the modified dry fuel obtained in the step (4) is conveyed to a fuel utilization unit to be utilized as fuel, the other part of the modified dry fuel is conveyed to a heat supply unit, sufficient air is introduced to combust under the coordination of auxiliary fuel, and the precipitate obtained in the step (2) and the baking gas obtained in the step (4) are also conveyed to the heat supply unit to participate in combustion to generate high-temperature flue gas; and (3) dividing the high-temperature flue gas generated by the heat supply unit into three paths by a flue gas distribution unit, providing required energy for the hydrothermal flue gas in the step (1), the drying flue gas in the step (3) and the baking flue gas in the step (4) respectively, connecting the residual flue gas generated by the flue gas distribution unit into a water storage device, and performing heat exchange on the residual flue gas and the water storage device to form normal-temperature waste flue gas for emission. The fuel utilization unit is a single or combined device of pyrolysis, gasification, combustion or other similar thermochemical processes.
Wherein: the hydrothermal flue gas and the dry flue gas adopt a circulation mode to indirectly exchange heat with the materials, the baking flue gas adopts a non-circulation mode, and the baking flue gas is introduced into the baking unit to directly exchange heat with the materials and then is converged into the baking gas. The flue gas distribution unit comprises a flue gas chamber, and a plurality of valves, fans, heat preservation main pipes and heat preservation branch pipes which are communicated with the flue gas chamber, so that distribution (circulation) and flow control of the flue gases (the hydrothermal flue gas in the step (1), the dry flue gas in the step (3) and the baking flue gas in the step (4)) are realized.
The invention provides a method for preparing modified dry fuel, which comprises the steps of dividing a part of the obtained modified dry fuel, matching with auxiliary fuel combustion, providing fuel for other necessary hydrothermal treatment units, drying units and baking units, basically realizing self-heating of the process, realizing reasonable distribution and utilization of energy due to the design of a flue gas distribution unit, avoiding energy waste to the maximum extent, and carrying out good treatment and recycling on generated byproducts such as slurry, baking gas and the like, thereby realizing cleanness and harmlessness of the whole process.
Further, the mass ratio of the modified dry fuel conveyed to the fuel utilization unit and the heat supply unit is greater than or equal to 9: 1.
Preferably, the high-nitrogen biomass waste in the step (1) is selected from more than one of sewage sludge, antibiotic fungi residues and peat.
Preferably, the hydrothermal treatment unit in step (1) includes at least 2 hydrothermal sealing kettles connected in parallel, the hydrothermal sealing kettles are connected with the inlets and the outlets in a same position through pipelines and valves to form a standby continuous operation unit, a hydrothermal flue is arranged on the outer side of the hydrothermal sealing kettle, a stirring device and a temperature measuring device are arranged in the hydrothermal sealing kettle, the hydrothermal flue is provided with a hydrothermal flue gas inlet and a hydrothermal flue gas outlet, and the hydrothermal flue gas inlet and the hydrothermal flue gas outlet are connected with the flue gas distribution unit.
Preferably, in the step (3), the drying unit is a vertical drying tower or a horizontal drying box, a drying flue is arranged outside the vertical drying tower, the drying flue extends towards the fuel channel to form a plurality of plate-type heat transfer channels, a drying flue gas outlet and a drying flue gas inlet are respectively arranged at the upper end and the lower end of the drying flue, the drying flue gas outlet and the drying flue gas inlet are connected with the flue gas distribution unit, the preliminary modified wet fuel enters from the fuel inlet at the upper end, moves downwards by means of gravity, and indirectly exchanges heat with the drying flue gas in a countercurrent manner to obtain the preliminary modified dry fuel, and the preliminary modified dry fuel is discharged from the.
Furthermore, a plurality of layers of horizontal belts driven by a transmission device are arranged in the horizontal drying box and are divided into a plurality of return fuel channels, a plurality of layers of parallel horizontal smoke pipes vertical to the horizontal belts are arranged on two sides of each return fuel channel, one end of each top smoke pipe is connected with a smoke outlet, one end of each bottom smoke pipe is connected with a smoke inlet, the smoke outlets and the smoke inlets are connected with a smoke distribution unit, reasonable flowing of smoke in the horizontal drying box is realized, the primarily modified wet fuel enters from the fuel inlet, is conveyed in a reciprocating mode through the horizontal belts from top to bottom in a multi-return mode and indirectly exchanges heat with smoke cross flow, and the primarily modified dry fuel is obtained and is discharged from the fuel outlet.
Preferably, the baking unit in the step (4) is a vertical baking furnace or a horizontal baking box which is isolated from air, when the baking unit is a vertical baking furnace, the primary modified dry fuel is conveyed in the vertical baking furnace by gravity, and through arranging a plurality of baffles, the full countercurrent direct heat exchange with the baking flue gas is realized, so that the baking gas and the modified dry fuel are obtained; when the baking unit is a horizontal baking box, the primary modified dry fuel is conveyed in the horizontal baking box by a belt transmission device, and the full countercurrent direct heat exchange with the baking flue gas is realized by arranging a plurality of layers of horizontal belts, so that the baking gas and the modified dry fuel are obtained.
Preferably, temperature measuring devices are arranged in the drying unit and the baking unit. The drying temperature is regulated and controlled through the flow of drying flue gas, and the baking temperature is regulated and controlled through the flow of baking flue gas.
Compared with the prior art, the invention has the following advantages:
(1) aiming at the characteristic that the high-nitrogen biomass waste contains considerable unstable nitrogen functional groups (inorganic nitrogen and easily decomposed protein nitrogen), the hydrothermal treatment and baking are carried out in sequence, so that the contained unstable nitrogen is decomposed and transferred to a liquid phase or a gas phase, the effective removal of the solid-phase fuel nitrogen is realized in two steps, and regarding the removal rate of the fuel nitrogen, the hydrothermal treatment unit is 40-55 percent and the baking unit is 25-40 percent, thereby effectively reducing the nitrogen from the fuel to the pollutant NO of the high-nitrogen biomass waste in the rear-end fuel utilization processxThe transformation of (3);
(2) in the process of the hydrothermal treatment and the baking process, organic functional groups with weak bond energy are easy to decompose firstly, such as dehydroxylation, decarboxylation and other reactions, so that the proportion of organic elements in the fuel is changed, the carbon and hydrogen content is obviously increased, and the oxygen content is reduced, therefore, the heat value of the dry-based fuel is increased to a certain extent in both the processes, the energy density of the fuel is improved, such as the dry-based heat value of unit fuel, the hydrothermal treatment unit is increased by 2-7%, and the baking unit is increased by 10-25%.
(3) Aiming at the characteristic of high water content of the high-nitrogen biomass waste, the hydro-thermal treatment is combined with the subsequent dehydration and drying processes, and the appropriate hydro-thermal conditions weaken the binding force of each functional group and each structure of the fuel on water molecules from multiple aspects, such as cell rupture release of combined water, removal of hydrophilic functional groups, hydrolysis reaction and the like, so that the water molecules are easier to remove or evaporate, the subsequent dehydration efficiency is improved, the subsequent drying energy consumption is reduced, and the treatment process from wet fuel to dry fuel is economic, convenient and efficient;
(4) the invention utilizes a part of the obtained modified dry fuel to shunt and cooperate with auxiliary fuel combustion to provide fuel for other necessary units, thereby basically realizing the self-heating of the process, and the design of the flue gas distribution unit realizes the reasonable distribution and utilization of energy, avoids the waste of energy to the greatest extent, and in addition, carries out good treatment and cyclic utilization on the generated byproducts, such as slurry, baking gas and the like, and realizes the cleanness and harmlessness of the whole process.
Description of the drawings:
FIG. 1 is a schematic process flow diagram of an upgrading denitrification modification method for utilizing high-nitrogen biomass waste as fuel according to the invention;
FIG. 2 is a schematic structural view of the hydrothermal treatment unit of FIG. 1;
FIG. 3 is a schematic diagram of a vertical drying tower of embodiment 1 of the drying unit of FIG. 1;
FIG. 4 is a schematic view of a horizontal drying box of embodiment 2 of the drying unit in FIG. 1;
FIG. 5 is a schematic view of a vertical roasting furnace according to embodiment 1 of the roasting unit in FIG. 1;
FIG. 6 is a schematic view of a horizontal torrefaction tank of embodiment 2 of the torrefaction unit of FIG. 1;
fig. 7 is a schematic structural view of the smoke distribution unit in fig. 1, wherein arrows in fig. 7 indicate the flow direction of smoke.
The specific implementation mode is as follows:
the following examples are further illustrative of the present invention and are not intended to be limiting thereof.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "horizontal", "top", "bottom", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, the terms "first", "second", "third", "fourth", "fifth" and "fifth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated, whereby the features defined as "first", "second", "third", "fourth" and "fifth" may explicitly or implicitly include at least one such feature.
Example 1:
as shown in fig. 1 to 7, the quality-improving denitrification modification method using high-nitrogen biomass waste as fuel includes a hydrothermal treatment unit, a dehydration unit, a drying unit, a baking unit, a heat supply unit, a flue gas distribution unit, a slurry treatment unit for balancing materials, and a water storage device, which modify the high-nitrogen biomass waste in sequence, and the method includes the following steps:
(1) under the thermal action of hydrothermal flue gas, after high-nitrogen biomass waste and softened water from a water storage device enter a hydrothermal treatment unit and are mixed, carrying out hydrothermal preliminary quality improvement and denitrification treatment to obtain preliminary modified slurry, wherein the temperature of the hydrothermal treatment unit is controlled to be 180-210 ℃, and the hydrothermal treatment time is 10 min;
(2) conveying the primary modified slurry obtained in the step (1) to a dehydration unit for dehydration treatment to obtain slurry and primary modified wet fuel, staying for 15min, conveying the slurry to a slurry treatment unit to obtain treatment liquid and precipitate, and returning the treatment liquid to the hydrothermal treatment unit in the step (1) for recycling;
(3) conveying the primary modified wet fuel obtained in the step (2) to a drying unit, and drying under the thermal action of dry flue gas to obtain primary modified dry fuel with the water content of less than 13%, wherein the temperature of the drying unit is controlled to be 85-110 ℃, and the drying time is 20 min;
(4) conveying the primary modified dry fuel obtained in the step (3) to a baking unit, and further carrying out quality improvement and denitrification treatment on the primary modified dry fuel under the thermal action of baking flue gas, wherein the temperature of the baking unit is controlled to be 250-300 ℃, and the baking retention time is 5min, so as to obtain baking gas and a product modified dry fuel;
(5) conveying most of the modified dry fuel to a fuel utilization unit for utilization, conveying a small part of the modified dry fuel to a heat supply unit, introducing sufficient air for combustion under the coordination of auxiliary fuel (branch materials or formed particles), and conveying the precipitate in the step (2) and the baking gas in the step (4) to the heat supply unit to participate in combustion; the high-temperature flue gas that the heat supply unit produced divides into three routes through the flue gas distribution unit, is the hydrothermal flue gas of step (1), (3) and (4), dry flue gas and the flue gas of baking respectively, provides hydrothermal processing unit, drying unit and the unit required energy of baking respectively, wherein: the hydrothermal flue gas and the dry flue gas adopt a circulation mode to indirectly exchange heat with the materials, the baking flue gas adopts a non-circulation mode, is introduced into the baking unit, directly exchanges heat with the materials, and then is converged into the baking gas. And the residual low-temperature flue gas generated by the flue gas distribution unit is connected into the water storage device, and after heat exchange, normal-temperature waste flue gas is formed and discharged. In this embodiment, the high-nitrogen biomass waste is sewage sludge.
In the step (1), since the high-nitrogen biomass waste is a high-moisture substance, the softened water is make-up water, and the mass ratio of the softened water to the high-nitrogen biomass waste is controlled within 10%, in this embodiment, the mass ratio of the softened water to the high-nitrogen biomass waste is 0.1, and the feed liquor of the hydrothermal treatment unit in each daily operation is set as: the mass ratio of the treatment liquid to the make-up water is 8:2, and the liquid inlet setting is changed every 10 times: the mass ratio of the treatment liquid to the make-up water is 2:8, and the treatment liquid with the mass fraction of 80 percent is discharged from the slurry treatment unit to be used as other purposes so as to ensure the balance of the concentration and the amount of organic matters and ammonia in the slurry.
The hydrothermal treatment unit in step (1) adopts at least two parallel hydrothermal sealed kettles, in this embodiment, two hydrothermal sealed kettles 2 are connected in parallel, as shown in fig. 2, a hydrothermal kettle cavity 27 is formed in each hydrothermal sealed kettle 2, the outer side of each hydrothermal sealed kettle is wrapped by a hydrothermal flue 26, and feeding, liquid inlet and discharging of hydrothermal flue gas on the two hydrothermal sealed kettles 2 are synchronously connected with the main feeding pipe 21, the main liquid inlet pipe 215, the flue gas distribution unit and the dehydration unit through the feeding pipe 22, the feeding valve 23, the liquid inlet pipe 24, the liquid inlet valve 25, the hydrothermal flue gas inlet 29, the hydrothermal flue gas outlet 212, the hydrothermal flue gas inlet valve 221, the hydrothermal flue gas outlet valve 222, the discharging pipe 210 and the discharging valve 211 respectively, so as to ensure continuous operation of the hydrothermal treatment unit. The hydrothermal seal kettle cavity 27 is internally provided with a stirring device 28, a first temperature measuring device 214 and a pressure measuring device 213 so as to ensure the reaction operating conditions. The main feed line 215 is controlled by a third valve 216, resulting from the mixing of a make-up water line 220 and a process liquid line 218, the proportions of which are controlled by a fifth valve 219 and a fourth valve 217, respectively. The nitrogen of the primary modified slurry fuel obtained by the hydrothermal treatment unit is reduced by 40-50%, and the unit dry basis heat value can be improved by 2-5%.
Dehydrating in a centrifugal dehydration mode adopted by a dehydration unit in the step (2), wherein the process condition is that the rotating speed is 1000-2500 rpm; the dehydration treatment time is 15min, and the water content of the primary modified wet fuel obtained by the dehydration unit is reduced to 50-55 percent.
In the step (3), the drying unit adopts a vertical drying tower in the embodiment, as shown in fig. 3, auxiliary air opposite to the primary modified wet fuel flows through the first fuel channel 35, the auxiliary air enters from the auxiliary air inlet 311 and is discharged from the auxiliary air outlet 312 to assist in the circulation of the steam generated by drying, the first fuel outlet 38 is provided with a second temperature measuring device 36, the temperature of the drying unit is maintained at 85-110 ℃, the drying time is 20min, and the moisture content of the primary modified dry fuel obtained by the drying unit is lower than 13%.
The outer side of the vertical drying tower 3 is provided with a drying flue 33, the upper end and the lower end of the drying flue 33 are respectively provided with a first drying flue gas outlet 32 and a first drying flue gas inlet 37 which are connected with a flue gas distribution unit, the drying flue 33 extends towards a first fuel channel 35 to form a plurality of plate-type heat transfer channels 39, each plate-type heat transfer channel 39 forms a certain angle with the horizontal direction and is fixed by a first supporting plate 310, in the embodiment, the number of the plate-type heat transfer channels 39 is 4, the plate-type heat transfer channels are uniformly distributed in the vertical direction of the vertical drying tower 3, and the angle with. The primary modified wet fuel enters from the first fuel inlet 31 at the upper end, moves downwards by means of gravity, and performs countercurrent indirect heat exchange with the dry flue gas to obtain the primary modified dry fuel, and the primary modified dry fuel is discharged from the first fuel outlet 38 at the lower end.
In step (4), the baking unit is an air isolation device, and in this embodiment, a vertical baking furnace is used, as shown in fig. 5. In the vertical baking furnace 5, the primary modified dry fuel enters from the third fuel inlet 51 at the top end, and is conveyed by gravity, the baking flue gas enters from the first baking flue gas inlet 57 at the bottom end, is in direct countercurrent contact with the primary modified dry fuel, and is discharged from the first baking gas outlet 58, a plurality of baffles 55 are uniformly distributed on the inner wall of the third fuel channel 54, the baffles 55 form 30-45 degrees with the horizontal direction, and are fixed by the second supporting plate 56, in the embodiment, the number of the baffles 55 is 4, and the feeding speed is adjusted by the arrangement of the baffles 55, so that the baking retention time is ensured, and the sufficient heat exchange is realized; the temperature measuring devices are arranged at the fuel inlet and the fuel outlet, the baking temperature is maintained at 250-300 ℃, the baking time is 5min through the adjustment and control of the flow rate of baking flue gas, baking gas and the modified dry fuel of the product are obtained through the baking unit, the modified dry fuel is discharged from the third fuel outlet 59, compared with the primary modified dry fuel, the water content of the modified dry fuel obtained through the baking unit process is lower than 5%, the fuel nitrogen is reduced by 25-30%, and the unit dry basis heat value is improved by 10-20%.
The flue gas distribution unit 1 in the step (5) is shown in fig. 7, and the flue gas distribution unit 1 comprises a main flue gas chamber 12, a high temperature chamber 15, a low temperature chamber 16, a dust collection chamber 14, a heat transfer plate 17 for isolating the high temperature chamber 15 from the low temperature chamber 16, and flue gas pipes, valves and fans which are conveyed to the units and reused. Under the action of the high-temperature fan 11, high-temperature flue gas from the heat supply unit enters the main flue gas chamber 12, large particle dust in the high-temperature flue gas enters the dust collection chamber 14 through sedimentation, the high-temperature flue gas in the main flue gas chamber 12 enters the high-temperature chamber 15, the high-temperature flue gas is divided into three strands of flue gas under the control of the flue pipe valves 110 and is respectively conveyed to the hydrothermal treatment unit, the drying unit and the baking unit through the second pipeline 111, low-temperature flue gas after indirect heat exchange between the hydrothermal treatment unit and the drying unit is returned to the low-temperature chamber 16 through the first pipeline 19, the flow rate is controlled by the first valve 18, then, the residual low-temperature flue gas in the low-temperature chamber 16 is conveyed to the water storage device through the third pipeline 112 for heat exchange, the flow rate is controlled by the second valve 113, and the heat transfer plate 17 can.
In the step (5), the mass ratio of the modified dry fuel conveyed to the fuel utilization unit and the heat supply unit is greater than or equal to 9:1, in the embodiment, the mass ratio of the modified dry fuel conveyed to the fuel utilization unit and the heat supply unit is preferably equal to 9:1, and the fuel utilization unit is a single or combined device of pyrolysis, gasification, combustion or other similar thermochemical processes.
In this embodiment, all the conveying pipelines, valves, furnace bodies, etc. related to the flue gas are subjected to heat preservation treatment (as shown in fig. 3 to 7, the first heat preservation wall 13, the second heat preservation wall 34, the third heat preservation wall 44, the fourth heat preservation wall 53, and the fifth heat preservation wall 63 are arranged), so as to reduce energy loss.
In summary, through continuous hydrothermal, dehydration, drying and baking treatment, appropriate process conditions of each unit are set according to the characteristics of sewage sludge, compared with the prior art, the dry-based calorific value of the modified fuel obtained by the method through coupling the sequence is increased by 12-26%, the nitrogen removal rate of the fuel is 55-65%, the moisture content is lower than 5%, the energy grade of the sewage sludge is effectively improved, the content of harmful components is reduced, and the high-efficiency clean thermochemical utilization of the rear end of the sewage sludge can be realized.
Example 2:
as shown in fig. 1 to 7, the difference is the same as that of embodiment 1: the high-nitrogen biomass waste is a mixture of antibiotic bacterial residues and peat, wherein the mass ratio of the antibiotic bacterial residues to the peat is 1: 1.
In the embodiment, the mass ratio of the softened water to the high-nitrogen biomass waste is 0.08, the hydrothermal treatment time is 60min, the nitrogen of the primary modified slurry fuel obtained by the hydrothermal treatment unit is reduced by 46-55%, and the unit dry basis heat value can be improved by 4-7%. The mass ratio of the modified dry fuel conveyed to the fuel utilization unit and the heat supply unit is 10:1, the dehydration unit adopts a mechanical filter pressing mode for dehydration, the pressure is 6MPa, the dehydration treatment time is 25min, and the moisture content of the primary modified wet fuel obtained by the dehydration unit is reduced to 55-60%.
The drying unit adopts a horizontal drying box, as shown in fig. 4, auxiliary air opposite to the direction of the primary modified wet fuel is introduced into a fuel channel, the auxiliary air enters from an auxiliary air inlet 411 and is discharged from an auxiliary air outlet 412 to assist the circulation of water vapor generated by drying, a third temperature measuring device 46 is arranged at a second fuel outlet 47, the temperature of the drying unit is maintained at 85-110 ℃, the drying treatment time is 30min, and the moisture content of the primary modified dry fuel obtained by the drying unit is lower than 13%.
The horizontal drying box 4 is internally provided with a plurality of layers of first horizontal belts 49 driven by a first transmission device 410 and divided into a plurality of return stroke second fuel channels 45, a plurality of layers of parallel horizontal smoke pipes 43 vertical to the first horizontal belts 49 are arranged on two sides of each return stroke second fuel channel 45, the adjacent layers of smoke pipes are reasonably connected, one end of a top layer smoke pipe is connected with a second dry smoke outlet 42, one end of a bottom layer smoke pipe is connected with a second dry smoke inlet 48, the second dry smoke inlet 48 and the second dry smoke outlet 42 are connected with a smoke distribution unit, so that the reasonable flow of the dry smoke in the horizontal drying box 4 is realized, the primary modified wet fuel enters from the second fuel inlet 41 at one end, is repeatedly conveyed by virtue of a plurality of return strokes from top to bottom by virtue of the first horizontal belts 49 and indirectly exchanges heat with the dry smoke in a cross flow manner to obtain the primary modified dry fuel, and is discharged from the second fuel outlet 47, in the embodiment, the, the two-pass second fuel channel 45 is divided, the parallel horizontal flue 43 is three-layer, and the reciprocating delivery of the fuel is two-pass.
In step (4), the baking unit is an air isolation device, and in this embodiment, a horizontal baking oven is adopted, as shown in fig. 6.
In the horizontal type baking box 6, the primary modified dry fuel enters from the fourth fuel inlet 61 at one end of the upper part, the second horizontal belt 65 driven by the second transmission device 66 is used for conveying, the baking flue gas enters from the second baking flue gas inlet 67 at one end of the lower part and is in direct contact with the primary modified dry fuel in a reverse flow mode, and then the baking flue gas is discharged from the second baking gas outlet 68, the second horizontal belt 65 is divided into a plurality of layers and can be divided into a plurality of return stroke fourth fuel channels 64, so that the primary modified dry fuel can reciprocate from top to bottom in a multi-return stroke mode, the embodiment is preferable, the second horizontal belt 65 is two layers, two fourth fuel channels 64 are divided, the primary modified dry fuel can reciprocate into two return strokes, the feeding speed is adjusted through the arrangement of the plurality of layers of second horizontal belts 65, so that the baking residence time is ensured. And fifth temperature measuring devices 62 are arranged at a fourth fuel inlet 61 and a fourth fuel outlet 69, the baking temperature is maintained at 250-300 ℃, the baking flue gas flow is regulated and controlled, the baking time is 10min, baking gas and a product modified dry fuel are obtained through a baking unit, the modified dry fuel is discharged from the fourth fuel outlet 69, compared with the primary modified dry fuel, the water content of the modified dry fuel obtained through the baking unit process is lower than 5%, the fuel nitrogen is reduced by 30-40%, and the unit dry basis heat value is improved by 15-25%.
In conclusion, aiming at the characteristics of antibiotic bacterial residues and peat, the two raw materials are reasonably proportioned and subjected to quality improvement and denitrification through a proper continuous hydrothermal, dehydration, drying and baking treatment coupling process, compared with the prior art, the dry basis calorific value of the modified fuel obtained by coupling the method in sequence is increased by 20-34%, the nitrogen removal rate of the fuel is 62-75%, the moisture content is reduced to below 5%, the quality of the fuel can be greatly improved, the nitrogen content of the fuel can be reduced, and the efficient and clean thermochemical utilization of the rear end of the fuel can be effectively realized.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, simplifications, etc., which are made without departing from the spirit and principle of the present invention, should be regarded as being equivalent to the replacement of the above embodiments, and are included in the scope of the present invention.

Claims (5)

1. A quality-improving denitrification modification method for utilizing high-nitrogen biomass waste as fuel is characterized by comprising the following steps:
(1) under the thermal action of hydrothermal flue gas, after high-nitrogen biomass waste and water enter a hydrothermal treatment unit to be mixed, carrying out hydrothermal preliminary quality improvement and denitrification treatment to obtain preliminary modified slurry, wherein the temperature of the hydrothermal treatment unit is controlled to be 180-210 ℃, the hydrothermal treatment time is 10-60 min, and the high-nitrogen biomass waste is selected from more than one of sewage sludge, antibiotic bacterial residues and peat; the hydrothermal treatment unit comprises at least 2 hydrothermal sealing kettles connected in parallel, the hydrothermal sealing kettles are connected with the inlets and the outlets in a same position through pipelines and valves to form a standby continuous operation unit, a hydrothermal flue is arranged on the outer side of each hydrothermal sealing kettle, a stirring device and a temperature measuring device are arranged in each hydrothermal sealing kettle, each hydrothermal flue is provided with a hydrothermal flue gas inlet and a hydrothermal flue gas outlet, and the hydrothermal flue gas inlets and the hydrothermal flue gas outlets are connected with a flue gas distribution unit;
(2) conveying the primary modified slurry obtained in the step (1) to a dehydration unit for dehydration treatment to obtain slurry and primary modified wet fuel, wherein the dehydration treatment time is 15-25 min, the slurry is conveyed to a slurry treatment unit to obtain treatment liquid and precipitates, and the treatment liquid is returned to the hydrothermal treatment unit in the step (1) to form recycling;
(3) conveying the primary modified wet fuel obtained in the step (2) to a drying unit, and drying under the thermal action of dry flue gas to obtain primary modified dry fuel with the water content of less than 13%, wherein the temperature of the drying unit is controlled at 85-110 ℃;
(4) conveying the primary modified dry fuel obtained in the step (3) to a baking unit, and further carrying out quality improvement and denitrification treatment on the primary modified dry fuel under the thermal action of baking flue gas, wherein the temperature of the baking unit is controlled to be 250-300 ℃, and the baking treatment time is 5-10 min, so as to obtain baking gas and a product modified dry fuel; temperature measuring devices are arranged in the drying unit and the baking unit;
conveying one part of the modified dry fuel obtained in the step (4) to a fuel utilization unit to be used as fuel, conveying the other part of the modified dry fuel to a heat supply unit, introducing sufficient air to combust under the cooperation of auxiliary fuel, conveying the precipitate obtained in the step (2) and the baking gas obtained in the step (4) to the heat supply unit, and combusting to generate high-temperature flue gas; and (3) dividing the high-temperature flue gas generated by the heat supply unit into three paths by a flue gas distribution unit, providing required energy for the hydrothermal flue gas in the step (1), the drying flue gas in the step (3) and the baking flue gas in the step (4) respectively, connecting the residual flue gas generated by the flue gas distribution unit into a water storage device, and performing heat exchange on the residual flue gas and the water storage device to form normal-temperature waste flue gas for emission.
2. The method for improving quality, removing nitrogen and modifying fuel utilization of high-nitrogen biomass waste as claimed in claim 1, wherein the mass ratio of the modified dry fuel conveyed to the fuel utilization unit and the heat supply unit is greater than or equal to 9: 1.
3. The method for upgrading, denitrifying and modifying high-nitrogen biomass waste used as fuel according to claim 1, wherein the drying unit in step (3) is a vertical drying tower or a horizontal drying box, a drying flue is arranged outside the vertical drying tower, the drying flue extends towards the fuel channel to form a plurality of plate-type heat transfer channels, the upper end and the lower end of the drying flue are respectively provided with a drying flue gas outlet and a drying flue gas inlet, the drying flue gas outlet and the drying flue gas inlet are connected with a flue gas distribution unit, and the primary modified wet fuel enters from the fuel inlet at the upper end, moves downwards by gravity, and indirectly exchanges heat with the drying flue gas in a countercurrent manner to obtain the primary modified dry fuel, and is discharged from the fuel outlet at the lower end.
4. The method for upgrading, denitrifying and modifying high-nitrogen biomass waste as fuel according to claim 3, wherein a plurality of layers of horizontal belts driven by a transmission device are arranged in the horizontal drying box and are divided into a multi-return fuel channel, a plurality of layers of parallel horizontal smoke tubes perpendicular to the horizontal belts are arranged on both sides of each return fuel channel, one end of each top smoke tube is connected with the smoke outlet, one end of each bottom smoke tube is connected with the smoke inlet, the smoke outlet and the smoke inlet are connected with the smoke distribution unit, so that reasonable flow of smoke in the horizontal drying box is realized, the primary modified wet fuel enters from the fuel inlet, is conveyed in a reciprocating manner by virtue of the multi-return channels from top to bottom by virtue of the horizontal belts, indirectly exchanges heat with smoke in a cross flow manner, and the primary modified dry fuel is obtained and discharged from.
5. The method for improving quality, removing nitrogen and modifying utilization of high-nitrogen biomass waste as fuel according to claim 1, wherein in the step (4), the baking unit is a vertical baking furnace or a horizontal baking box which is isolated from air, when the baking unit is a vertical baking furnace, the primary modified dry fuel is conveyed in the vertical baking furnace by gravity, and through arranging a plurality of baffles, the full countercurrent direct heat exchange with the baking flue gas is realized to obtain the baking gas and the modified dry fuel; when the baking unit is a horizontal baking box, the primary modified dry fuel is conveyed in the horizontal baking box by a belt transmission device, and the full countercurrent direct heat exchange with the baking flue gas is realized by arranging a plurality of layers of horizontal belts, so that the baking gas and the modified dry fuel are obtained.
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