CN108929737A - Biomass solid clean fuel and its preparation method and application - Google Patents
Biomass solid clean fuel and its preparation method and application Download PDFInfo
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- CN108929737A CN108929737A CN201810679644.6A CN201810679644A CN108929737A CN 108929737 A CN108929737 A CN 108929737A CN 201810679644 A CN201810679644 A CN 201810679644A CN 108929737 A CN108929737 A CN 108929737A
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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
- C10L5/46—Solid fuels essentially based on materials of non-mineral origin on sewage, house, or town refuse
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- 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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Abstract
The invention discloses a kind of biomass solid clean fuels and its preparation method and application, the atomic percentage of carbon is 37.15%~50.24% in the biomass solid clean fuel, higher calorific value is the MJ/kg of 13.50 MJ/kg~22.22, it is made by following methods: hot-forming after preprocessed, soda acid processing and hydro-thermal charing process to be made using sludge and biomass castoff as raw material.Biomass solid clean fuel of the present invention have many advantages, such as carbon content is high, nitrogen content is low, calorific value is high, pollution less, prepare it is simple and easy, low in cost, a kind of clean new material, preparation method have many advantages, such as preparation process is simple and easy, low in cost, energy consumption less, time-consuming is short, condition is easily-controllable.Biomass solid clean fuel of the present invention is used for burned for energy as fuel, have many advantages, such as that easy to operate, energy conversion efficiency is high, secondary pollution is few, it can be achieved that biomass solid clean fuel energy clean utilization.
Description
Technical field
The invention belongs to solid fuel field, it is related to a kind of biomass solid clean fuel and its preparation method and application.
Background technique
City sewage and sludge is the solid waste generated in sewage disposal process, has moisture content height, content of beary metal
The features such as high and bacterial content is high, thus be difficult to handle.Nowadays, 80% or more sludge is still by compressing dehydration-landfill
Conventional method is handled, and these conventional process modes have had resulted in serious secondary pollution and discharged a large amount of greenhouse gas
Body counteracts the emission reduction effect of sewage treatment significantly, and specific resistance to filtration is made to face the dual of prevention of secondary pollution and carbon emission reduction
Pressure.Moreover, building up with more sewage treatment plants, generated sewage sludge will also increase day by day.For this purpose, with
The increase of population, the urbanization quickly propelled and process of industrialization are difficult to reduce municipal sewage dirt on a large scale in economy, technology
Mud amount.Organic matter content is abundant in sludge, is a kind of valuable source, this viewpoint has worldwide obtained sufficiently
Understanding.Traditional recycling sludge using processing method have it is aerobic disappear, anaerobic digestion, burning, landfill and agricultural use etc.,
These processing methods do not make full use of not only sludge as the huge resource value of biomass, cause to environment huge yet
Harm, and it is incompatible with current energy policy.Therefore, how in field of resource utilization of sludge new, effective approach is opened up,
Find can make full use of sludge be worth and environmental pollution, reduce the sector carbon emission treatment process gesture must
Row.
On the other hand, China's biomass castoff disposition is started late, the biomass castoff recycling benefit of independent research
It is also being constantly improve with technology.Main raw material(s) of the biomass castoff as biomass energy, this viewpoint is in the world
Sufficient understanding has been obtained in range.Biomass castoff recycling should be that one kind can be used as substitution non-renewable energy resources and solve
The processing technique of energy development demand.And novel biomass castoff recovery energy technology is developed, it is not only to solve biology
The critical issue of matter offal treatment hardly possible, the problem of being also able to solve its energy clean utilization.
Currently, in the technology for preparing solid fuel as raw material using sludge or biomass castoff three classes can be roughly divided into:
First is that being directly compressible into type after sludge or biomass castoff are mixed desiccation with auxiliary material；Second is that first by sludge or biomass
Waste desiccation mixes compression forming with auxiliary material again；Third is that sludge or biomass castoff are directly mixed with auxiliary material
Desiccation again after compression forming.Auxiliary material (usually coal, calcium hypochlorite, the sodium hypochlorite being added are required in these three technologies
Deng) increase the calorific value of solid fuel or the dehydration rate of promotion solid fuel.Although solid fuel can be mentioned in nature certain
Height, but due to also joined the pollution elements such as chlorine, sulphur while these auxiliary materials are added, so that thus obtained solid
Fuel can discharge toxic and harmful gas in burning, be easy to cause secondary pollution.In addition, the solid fuel in actual fabrication process
Also easily there is the problems such as absorbing water again, difficult forming, low quality.
New technology of the hydro-thermal reaction technology as processing biomass castoff, can be converted to biomass energy for waste
Source.Hydro-thermal reaction can be divided into hydro-thermal gasification (HTG), hydrothermal liquefaction (HTL) and hydro-thermal charing according to the difference of reaction condition
(HTC).Biomass water is thermal evaporation can to generate methane and hydrogen, and hydrothermal liquefaction can produce glucide and its ramification, organic acid
And phenols (bio oil), the main powdery solid for generating similar coal type of hydro-thermal charing.Hydro-thermal gasification and hydrothermal liquefaction need
It is carried out under high-temperature and high-pressure conditions, if being used for Treatment of Sludge, energy consumption is high, and economic benefit is not significant.However, about biomass by hydro-thermal
Charing prepares the research of solid fuel in China still in the initial stage, and different types of High water cut is directed in existing research
Rate organic solid castoff, response parameter used by hydro-thermal carbonizes is not quite similar, while producing after hydro-thermal charing process
Raw product liquid not only will increase processing cost, while also will increase and causing secondary pollution there is still a need for secondary treatment is carried out
Risk.In addition, the research about sludge joint biomass castoff hydro-thermal charing is fewer and fewer, it can be effectively sharp there are no finding
The method for preparing solid cleaning fuel with sludge joint biomass castoff.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, provide a kind of carbon content is high, nitrogen content is low,
Calorific value is high, pollution less, low-cost biomass solid clean fuel and its preparation method and application.
In order to solve the above technical problems, the technical solution adopted by the present invention is that:
A kind of biomass solid clean fuel, the biomass solid clean fuel are with sludge and biomass castoff for original
Material, it is hot-forming after preprocessed, soda acid processing and hydro-thermal charing process to be made；Carbon in the biomass solid clean fuel
Atomic percentage is 37.15%~50.24%；The higher calorific value of the biomass solid clean fuel be 13.50 MJ/kg~
22.22 MJ/kg。
As a general technical idea, the present invention also provides a kind of preparation method of biomass solid clean fuel,
The following steps are included:
S1, biomass castoff is mixed with sludge, is stirred evenly, obtain sludge based biomass feedstock；
The pH value of sludge based biomass feedstock obtained in S2, regulating step S1 is 6~8, stirring, obtains sludge based biomass acid
Change/alkalization raw material；
S3, sludge based biomass obtained in step S2 is acidified/is alkalized raw material progress hydro-thermal carbonization reaction, gained hydrothermal carbonization
Product after reaction through separation of solid and liquid, freeze-day with constant temperature, pulverize, obtain sludge based biomass solid carbon powder raw material；
It is S4, sludge based biomass solid carbon powder raw material obtained in step S3 is hot-forming, obtain biomass solid cleaning combustion
Material.
Above-mentioned preparation method, it is further improved, in the step S1, the quality of the biomass castoff and sludge
Than being 1: 8~10；The revolving speed of the stirring is the r/min of 80 r/min~120.
Above-mentioned preparation method, further improved, in the step S1, the biomass castoff is sawdust, corn
At least one of stalk, corncob and rape stalk；The sludge is municipal sewage plant's residue dewatered sludge；The dirt
The moisture content of mud is 80%~90%.
Above-mentioned preparation method, further improved, in the step S1, the biomass castoff is mixed with sludge
It before further include drying and pulverizing processing；The temperature of the drying is 40 DEG C~70 DEG C；The time of the drying is for 24 hours；It is described
Pulverizing to be crushed to partial size is 1mm or less.
Above-mentioned preparation method, it is further improved, in the step S2, using acid or lye regulating step S1 in obtain
Sludge based biomass feedstock pH value；The acid is acetum；The mass concentration of the acetum is 36%~38%；Institute
Stating lye is sodium hydroxide solution；The molar concentration of the sodium hydroxide solution is 0.1mol/L~1mol/L；The stirring
Revolving speed is the r/min of 80 r/min~120；The time of the stirring is 1h~3h.
Above-mentioned preparation method, further improved, in the step S3, the hydro-thermal carbonization reaction is in nitrogen atmosphere
Under 220 DEG C~300 DEG C reaction 30min~4h are warming up to 5 DEG C/min~10 DEG C/min heating rate；The separation of solid and liquid is adopted
The miillpore filter for being 0.45 μm~1 μm with aperture；The temperature of the freeze-day with constant temperature is 105 DEG C~110 DEG C；The freeze-day with constant temperature
Time is for 24 hours~36h.
Above-mentioned preparation method, it is further improved, it is further comprising the steps of before the hydro-thermal carbonization reaction: by sludge
Based biomass is acidified/alkalizes raw material and is transferred in reaction kettle, is passed through with the flow velocity of 10mL/min~30mL/min into reaction kettle
Nitrogen 3min~5min empties the air in reaction kettle, continues to be passed through nitrogen until air pressure reaches 0.1MPa~0.5MPa；It is described
Reaction kettle is high-temperature high-pressure reaction kettle.
Above-mentioned preparation method, it is further improved, it is described hot-forming using hot-forming dress in the step S4
It sets；It is described hot-forming in the process controlled at 120 DEG C~140 DEG C；It is described it is hot-forming during, the hot-forming institute of single
The quality for needing raw material is 0.8g~1g, and pressure is the kN of 2 kN~4, and the duration is 30s~40s.
As a general technical idea, the present invention also provides a kind of above-mentioned biomass solid clean fuels or above-mentioned
Preparation method made from application of the biomass solid clean fuel in burned for energy.
Compared with the prior art, the advantages of the present invention are as follows:
(1) the present invention provides a kind of biomass solid clean fuels is located in advance using sludge and biomass castoff as raw material
It is hot-forming after reason, soda acid processing and hydro-thermal charing process to be made, consolidated by the way that biomass is made in sludge and biomass castoff
Body clean fuel realizes the resource utilization to sludge and biomass castoff, and the biomass solid clean fuel has
Carbon content is high, nitrogen content is low, calorific value is high, pollutes less, prepares the advantages that simple and easy, low in cost.Compared to existing biomass
The phosphorus content of solid fuel, biomass solid clean fuel of the present invention is higher, and calorific value is higher, this makes biomass solid of the present invention
Clean fuel can generate higher energy, and the content for the generated nitrogenous polluted gas that burns is lower, be that one kind cleans very much
New energy material.
(2) in biomass solid clean fuel of the invention, when using corncob as biomass castoff, biomass obtained
The higher calorific value of solid cleaning fuel is highest, up to 22.22MJ/kg, calorific value with higher；It is made a living physical obsolescence with sawdust
When object, the nitrogen content of biomass solid clean fuel obtained be it is minimum, only 2.09%, there is lower nitrogen content.
(3) the present invention also provides a kind of preparation methods of biomass solid clean fuel, first by sludge (moisture content is high)
It is sufficiently mixed with biomass castoff (water content is low), it is (useless by optimization sludge and biomass to obtain sludge based biomass feedstock
The proportion of gurry, so that the sludge based biomass feedstock has more suitable water content)；Raw material is under suitable pH environment
It is reacted, the formation porous structure that solid can be easier to, promotes solid product density, and then improve carbon content and calorific value.If
PH is excessively high or the too low formation that will increase ash content in reactant, therefore passes through acid or lye conditioning of mud based biomass feedstock
PH value is 6~8, this is conducive to the carbon sequestration content that material is improved in subsequent processes；Using hydro-thermal charing method by sludge
Based biomass is acidified/alkalizes raw material and carries out carbonization treatment, is fixed on carbon containing matter in solid product, while nitrogen substance being turned
It moves in liquid phase, not only increases the phosphorus content in solid, also reduce nitrogen material content in solid, to be released in burning
Less nitrogenous polluted gas is put, the burst size of toxic and harmful gas is reduced, reduces secondary pollution risk；Finally by being hot pressed into
Biomass solid clean fuel is made in type.As it can be seen that preparation method of the present invention can handle sludge and biomass castoff simultaneously, greatly
Reduce processing cost greatly, improve treatment effeciency, have preparation process is simple and easy, low in cost, energy consumption less, it is time-consuming it is short,
The advantages that condition is easily-controllable is suitable for continuous large-scale serial production, is convenient for industrialized utilization.In addition, existing other methods are compared, this
Biomass solid clean fuel made from invention preparation method, calorific value can be improved 1.02 times~1.10 times, and nitrogen content can reduce
55.23%~63.28%, have many advantages, such as high heating value, low pollution.
(4) in preparation method of the present invention, the abandoned biomass that sludge is huge as a kind of yield, moisture content is high, Neng Gouyu
Low water content biomass castoff complementation moisture, so that the sludge based biomass feedstock has more suitable water content,
And by optimization reaction condition control hydro-thermal charing, while generating solid cleaning fuel realization prevention and cure of pollution, carbon emission reduction and
The multiple benefits such as recycling.In the present invention, the hydro-thermal charing method of use can be by the mixture of sludge and biomass castoff
It is converted to the solid cleaning fuel that carbon content is high, functional group is abundant, calorific value is high, while the hydro-thermal charing method also has not by object
Expect the restriction of moisture content, the advantages that device procedures are simple, reaction condition is mild.
(5) application the present invention also provides a kind of biomass solid clean fuel in burned for energy, with this hair
Bright biomass solid clean fuel as fuel be used for burned for energy, have it is easy to operate, energy conversion efficiency is high, two
The advantages that secondary pollution is few, it can be achieved that biomass solid clean fuel energy clean utilization.Such as, by biomass solid of the present invention
When clean fuel is used to burn, highest calorific value, up to 22.22MJ/kg.
Detailed description of the invention
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical scheme in the embodiment of the invention is clearly and completely described.
Fig. 1 is the thermogravimetric analysis figure of biomass solid clean fuel obtained in the embodiment of the present invention 1.
Fig. 2 is the thermogravimetric analysis figure of biomass solid clean fuel obtained in the embodiment of the present invention 2.
Fig. 3 is the thermogravimetric analysis figure of biomass solid clean fuel obtained in the embodiment of the present invention 3.
Fig. 4 is the thermogravimetric analysis figure of biomass solid clean fuel obtained in the embodiment of the present invention 4.
Fig. 5 is biomass solid clean fuel (SS-SD, SS-CC, SS-CS, SS- obtained in 1-4 of the embodiment of the present invention
RS the comparison diagram of carbon, nitrogen percentage composition in).
Fig. 6 is a high position for biomass solid clean fuel (SS-SD, SS-CC, SS-CS, SS-RS) in the embodiment of the present invention 5
Calorific value comparison diagram.
Specific embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
It limits the scope of the invention.
Material employed in following embodiment and instrument are commercially available.In the embodiment of the present invention, unless otherwise noted,
Used technique is common process, and used equipment is conventional equipment, and following the data obtained is to test more than three times
Average value.
Embodiment 1:
A kind of biomass solid clean fuel, the biomass solid clean fuel are that (municipal sewage plant's residue is de- with sludge
Sewage sludge) and biomass castoff (sawdust) be raw material, hot-forming system after the processing of preprocessed, soda acid and hydro-thermal charing process
, the atomic percentage of carbon is 41.70% in obtained biomass solid clean fuel, and the atomic percentage of nitrogen is 2.09%；
The higher calorific value of the biomass solid clean fuel can reach 17.70MJ/kg.
A kind of preparation method of biomass solid clean fuel in above-mentioned the present embodiment, comprising the following steps:
(1) sludge and biomass castoff pre-process:
(1.1) it is dried after cleaning sawdust, it is 24 hours dry specially at 40 DEG C；Sawdust after will be dried pulverized
1mm sieve.
(1.2) sludge (municipal sewage treatment of the sawdust and 100g, moisture content 90% in 10g step (1.1) after sieving is taken
Factory's residue dewatered sludge) mixing, it is stirred until homogeneous under conditions of revolving speed is 100 r/min, obtains sludge based biomass feedstock.
(2) soda acid is handled:
(2.1) acid-base property of the sludge based biomass feedstock obtained in pH tester measuring process (1.2), if raw material pH value >
6 using acetum as pH adjusting agent, using sodium hydroxide solution as pH adjusting agent if < 6.
(2.2) the sodium hydroxide solution tune that mass concentration is 0.1mol/L for 36% acetum or molar concentration is used
The pH value for saving sludge based biomass feedstock obtained in step (1.2) is 6, and stirring 1 is small under conditions of revolving speed is 100r/min
When, it is uniformly mixed, obtains sludge based biomass and be acidified/alkalize raw material.
In the present invention, the pH of sludge based biomass feedstock is adjusted, the technical solution being not limited only in step (2), other
It can be realized the technical solution that the pH of sludge based biomass feedstock is adjusted to 6~8 by the present invention, it is feasible.
(3) hydro-thermal charing process:
Raw material is acidified/alkalizes by sludge based biomass obtained in step (2) to be transferred into high-temperature high-pressure reaction kettle (commercially available), with
Flow velocity is that 10mL/min is passed through nitrogen 5 minutes, empties the air in reaction kettle, continues to be passed through nitrogen until air pressure reaches
0.5MPa, i.e. the guarantee initial pressure of reaction kettle are 0.5MPa；Then under nitrogen atmosphere with the rate of 10 DEG C/min by reaction kettle
In temperature be warming up to 300 DEG C of progress hydro-thermal carbonization reactions, residence time 60min, the pressure during hydro-thermal carbonization reaction
For spontaneous pressure；Natural cooling after reaction, take out reaction gained mix products, via hole diameter be 0.45 μm miillpore filter into
Row is separated by solid-liquid separation, and obtained solid freeze-day with constant temperature 24 hours at 105 DEG C are pulverized, and obtains sludge based biomass solid carbon powder raw material.
(4) solid fuel is hot-forming:
Quality by single raw material needed for hot-forming is 1g, by sludge based biomass solid carbon dust obtained in 1g step (3)
Raw material is placed in heat pressing forming device, is 120 DEG C, is compressed 30s under pressure 4kN in forming temperature, passes through hot-forming obtained life
Material solid clean fuel, number SS-SD.
In the present invention, heat pressing forming device used includes following components: the solid work of diameter 6.3mm, high 90mm
Cylinder, the hollow cylinder of interior diameter 6.35mm, 70mm high are filled in, and is centered around the heating coil of hollow cylinder outer surface, is pressed
Force test device (MTI equipment Measurement Technology, Inc., Roswell, GA).In use process,
Sludge based biomass solid carbon powder raw material is placed in hollow cylinder, with solid piston cylinder to sludge base biology in hollow cylinder
Matter solid carbon powder raw material carry out it is hot-forming, it is hot-forming during by be centered around hollow cylinder outer surface heating coil and
Pressure test device controls temperature and pressure, is hot pressed into realize to sludge based biomass solid carbon powder raw material
Type obtains biomass solid clean fuel of the present invention.
In the present invention, to hot-forming, the technology being not limited only in step (4) of sludge based biomass solid carbon powder raw material
Scheme, other can be realized the present invention and the hot-forming biomass solid that is made of sludge based biomass solid carbon powder raw material cleaned combustion
The technical solution of material, it is feasible.
Embodiment 2:
A kind of biomass solid clean fuel, the biomass solid clean fuel are that (municipal sewage plant's residue is de- with sludge
Sewage sludge) and biomass castoff (corncob) be raw material, it is hot-forming after the processing of preprocessed, soda acid and hydro-thermal charing process
It is made, the atomic percentage of carbon is 50.13% in obtained biomass solid clean fuel；The biomass solid clean fuel
Higher calorific value be 22.22MJ/kg.
The preparation method of biomass solid clean fuel in a kind of above-mentioned the present embodiment, with the preparation side in embodiment 1
Method is compared, and difference is: in step (1), biomass castoff is corncob；In step (2), pH value is adjusted to 7；Step (3)
In, the temperature in reaction kettle is 260 DEG C.
Biomass solid clean fuel obtained, number SS-CC in the embodiment of the present invention 2.
Embodiment 3:
A kind of biomass solid clean fuel, the biomass solid clean fuel are that (municipal sewage plant's residue is de- with sludge
Sewage sludge) and biomass castoff (corn stover) be raw material, be hot pressed into after the processing of preprocessed, soda acid and hydro-thermal charing process
Type is made, and the atomic percentage of carbon is 37.45% in obtained biomass solid clean fuel；Biomass solid cleaning combustion
The higher calorific value of material is 15.92MJ/kg.
The preparation method of biomass solid clean fuel in a kind of above-mentioned the present embodiment, with the preparation side in embodiment 1
Method is compared, and difference is: in step (1), biomass castoff is corn stover；In step (2), pH value is adjusted to 7；Step
(3) in, the temperature in reaction kettle is 260 DEG C.
Biomass solid clean fuel obtained, number SS-CS in the embodiment of the present invention 3.
Embodiment 4:
A kind of biomass solid clean fuel, the biomass solid clean fuel are that (municipal sewage plant's residue is de- with sludge
Sewage sludge) and biomass castoff (rape stalk) be raw material, be hot pressed into after the processing of preprocessed, soda acid and hydro-thermal charing process
Type is made, and the atomic percentage of carbon is 39.37% in obtained biomass solid clean fuel；Biomass solid cleaning combustion
The higher calorific value of material is 17.16MJ/kg.
The preparation method of biomass solid clean fuel in a kind of above-mentioned the present embodiment, with the preparation side in embodiment 1
Method is compared, and difference is: in step (1), biomass castoff is rape stalk；In step (2), pH value is adjusted to 8；Step
(3) in, the temperature in reaction kettle is 260 DEG C.
Biomass solid clean fuel obtained, number SS-RS in the embodiment of the present invention 4.
Embodiment 5:
A kind of application of biomass solid clean fuel in burned for energy, comprising the following steps:
Biomass solid clean fuel (SS-SD, SS-CC, SS-CS, SS-RS) obtained in Example 1-4, each 15mg, point
It is not put into thermogravimetric analyzer and burns, burning gases used is air, and gas flow rate is set as 5mL/min, test biology
Matter solid cleaning fuel weight course in combustion, as a result as shown in Figs 1-4.
Biomass solid clean fuel (SS-SD, SS-CC, SS-CS, SS-RS) obtained in Example 1-4, each 10g,
It is respectively put into calorimeter, is filled with oxygen and burns, stablize to pressure gauge on oxygenating instrument in 3kPa, continue at least 15 seconds, survey
The higher calorific value of biomass solid clean fuel is tried, as a result as shown in Figure 5.
Fig. 1 is the thermogravimetric analysis figure of biomass solid clean fuel obtained in the embodiment of the present invention 1.In Fig. 1,1 institute is put
Corresponding temperature is temperature when burn rate is most fast in combustion, and temperature corresponding to point 2 is temperature of initial decomposition, point
3 be point 1 tangent line and cross point 2 extended lines focus, corresponding to temperature can be counted as ignition temperature.In conjunction with Fig. 1
In result and through analysis as can be seen that biomass solid clean fuel of the present invention weight reduces 52% after combustion, main combustion
Burning temperature range is 200 DEG C~500 DEG C, and at 408 DEG C, burn rate reaches maximum, illustrates that substance decomposition is most at such a temperature
It is more, also illustrate to have formd part fixed carbon in the solid fuel after hydro-thermal carbonizes, ignition temperature is 313 DEG C, compared to original
Expect more stable.
Fig. 2 is the thermogravimetric analysis figure of biomass solid clean fuel obtained in the embodiment of the present invention 2.In Fig. 2,1 institute is put
Corresponding temperature is temperature when burn rate is most fast in combustion, and temperature corresponding to point 2 is temperature of initial decomposition, point
3 be point 1 tangent line and cross point 2 extended lines focus, corresponding to temperature can be counted as ignition temperature.In conjunction with Fig. 2
In result and through analysis as can be seen that the present invention using corncob as biomass solid clean fuel made from biomass castoff
Weight reduces 58% after combustion, and primary combustion temperature range is 210 DEG C~530 DEG C, and at 470 DEG C, burn rate reaches most
Greatly, due in the biomass solid clean fuel primary combustion substance be volatile matter and fixed carbon, burn at such a temperature
Rate maximum illustrates to fix carbon content in the biomass solid clean fuel higher, and ignition temperature is 349 DEG C, illustrates the present invention
Biomass solid clean fuel is more stable than raw material (corncob).
Fig. 3 is the thermogravimetric analysis figure of biomass solid clean fuel obtained in the embodiment of the present invention 3.In Fig. 3,1 institute is put
Corresponding temperature is temperature when burn rate is most fast in combustion, and temperature corresponding to point 2 is temperature of initial decomposition, point
3 be point 1 tangent line and cross point 2 extended lines focus, corresponding to temperature can be counted as ignition temperature.In conjunction with Fig. 3
In result and through analysis as can be seen that the present invention using corn stover be biomass solid made from biomass castoff cleaning combustion
Weight reduces 53% to material after combustion, and primary combustion temperature range is 200 DEG C~520 DEG C.At 450 DEG C, burn rate reaches
Maximum is fired at such a temperature since primary combustion substance is volatile matter and fixed carbon in the biomass solid clean fuel
It burns rate maximum and illustrates to fix carbon content in the biomass solid clean fuel higher, ignition temperature is 331 DEG C, illustrates this hair
Open-birth material solid clean fuel is relatively stable, and compares raw material (corn stover), and stability significantly improves.
Fig. 4 is the thermogravimetric analysis figure of biomass solid clean fuel obtained in the embodiment of the present invention 4.In Fig. 4,1 institute is put
Corresponding temperature is temperature when burn rate is most fast in combustion, and temperature corresponding to point 2 is temperature of initial decomposition, point
3 be point 1 tangent line and cross point 2 extended lines focus, corresponding to temperature can be counted as ignition temperature.In conjunction with Fig. 4
In result and through analysis as can be seen that the present invention using rape stalk be biomass solid made from biomass castoff cleaning combustion
Weight reduces 46% to material after combustion, and primary combustion temperature range is 200 DEG C~520 DEG C.At 440 DEG C, burn rate reaches
Maximum, similarly, since primary combustion substance is volatile matter and fixed carbon in the biomass solid clean fuel, in the temperature
Lower burn rate maximum illustrates to fix carbon content in the biomass solid clean fuel higher, and ignition temperature is 336 DEG C, explanation
Biomass solid clean fuel of the present invention is relatively stable, and compares raw material (rape stalk), and stability significantly improves.
Member is carried out to biomass solid clean fuel (SS-SD, SS-CC, SS-CS, SS-RS) obtained in embodiment 1-4
Element analysis, result are as shown in Figure 5.Fig. 5 be biomass solid clean fuel obtained in 1-4 of the embodiment of the present invention (SS-SD,
SS-CC, SS-CS, SS-RS) in carbon, nitrogen relative content comparison diagram.As shown in Figure 5, after hydro-thermal carbonization reaction, this hair
Phosphorus content in open-birth material solid clean fuel is all improved, wherein using sludge (SS) and corncob as the biology of raw material
Carbon content highest in matter solid cleaning fuel, reaches 50.13%.Due to the relative increase of phosphorus content, biomass solid clean fuel
Middle fixed carbon component can also be increase accordingly, and ignition temperature is higher compared to raw material at this time, thus biomass solid clean fuel is more
Stablize, wherein carbon content highest, i.e., more stable performance are best in biomass solid clean fuel obtained in embodiment 2；Meanwhile
Carbon content is high, also illustrates that material has higher higher calorific value.In addition, nitrogen substance is in the meeting after hydro-thermal carbonization reaction in raw material
It is transferred in liquid phase or gas-phase product, thus nitrogen content can decrease in solid, this advantageously reduces biomass solid cleaning
The burst size of fuel nitrogenous polluted gas in burning, reduces a possibility that causing secondary pollution to ecological environment, wherein with
Sludge and sawdust are that nitrogen content is minimum in the biomass solid clean fuel of raw material, are 2.09%, discharge nitrogenous polluted gas
A possibility that amount is less, causes secondary pollution to ecological environment is minimum.
Fig. 6 is a high position for biomass solid clean fuel (SS-SD, SS-CC, SS-CS, SS-RS) in the embodiment of the present invention 5
Calorific value comparison diagram.It will be appreciated from fig. 6 that compare sludge (SS), biomass solid clean fuel of the present invention (SS-SD, SS-CC, SS-CS,
SS-RS higher calorific value (HHV)) has all obtained different degrees of raising, wherein using sludge and corncob as the biomass of raw material
Solid cleaning fuel (SS-CC) has highest calorific value, up to 22.22MJ/kg.
Above embodiments are only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned reality
Apply example.All technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It is noted that being led for this technology
For the those of ordinary skill in domain, improvements and modifications without departing from the principle of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of biomass solid clean fuel, which is characterized in that the biomass solid clean fuel is with sludge and biology
Matter waste is raw material, hot-forming after preprocessed, soda acid processing and hydro-thermal charing process to be made；The biomass solid is clear
The atomic percentage of carbon is 37.15%~50.24% in clean fuel；The higher calorific value of the biomass solid clean fuel is
The MJ/kg of 13.50 MJ/kg~22.22.
2. a kind of preparation method of biomass solid clean fuel, which comprises the following steps:
S1, biomass castoff is mixed with sludge, is stirred evenly, obtain sludge based biomass feedstock；
The pH value of sludge based biomass feedstock obtained in S2, regulating step S1 is 6~8, stirring, obtains sludge based biomass acid
Change/alkalization raw material；
S3, sludge based biomass obtained in step S2 is acidified/is alkalized raw material progress hydro-thermal carbonization reaction, gained hydrothermal carbonization
Product after reaction through separation of solid and liquid, freeze-day with constant temperature, pulverize, obtain sludge based biomass solid carbon powder raw material；
It is S4, sludge based biomass solid carbon powder raw material obtained in step S3 is hot-forming, obtain biomass solid cleaning combustion
Material.
3. preparation method according to claim 2, which is characterized in that in the step S1, the biomass castoff with
The mass ratio of sludge is 1: 8~10；The revolving speed of the stirring is the r/min of 80 r/min~120.
4. preparation method according to claim 3, which is characterized in that in the step S1, the biomass castoff is
At least one of sawdust, corn stover, corncob and rape stalk；The sludge is that residue dehydration in municipal sewage plant's is dirty
Mud；The moisture content of the sludge is 80%~90%.
5. the preparation method according to claim 4, which is characterized in that in the step S1, the biomass castoff exists
It further include drying and pulverizing processing before being mixed with sludge；The temperature of the drying is 40 DEG C~70 DEG C；The time of the drying
For for 24 hours；Described pulverize to be crushed to partial size is 1mm or less.
6. the preparation method according to any one of claim 2~5, which is characterized in that in the step S2, using acid or
The pH value of sludge based biomass feedstock obtained in lye regulating step S1；The acid is acetum；The acetum
Mass concentration is 36%~38%；The lye is sodium hydroxide solution；The molar concentration of the sodium hydroxide solution is 0.1mol/
L~1mol/L；The revolving speed of the stirring is the r/min of 80 r/min~120；The time of the stirring is 1h~3h.
7. the preparation method according to any one of claim 2~5, which is characterized in that in the step S3, the hydro-thermal
Carbonization reaction is to be warming up to 220 DEG C~300 DEG C reactions in a nitrogen atmosphere with 5 DEG C/min~10 DEG C/min heating rate
30min~4h；The separation of solid and liquid uses aperture for 0.45 μm~1 μm of miillpore filter；The temperature of the freeze-day with constant temperature is 105
DEG C~110 DEG C；The time of the freeze-day with constant temperature is for 24 hours~36h.
8. preparation method according to claim 7, which is characterized in that further include following step before the hydro-thermal carbonization reaction
It is rapid: sludge based biomass being acidified/alkalized raw material and is transferred in reaction kettle, with the past reaction of the flow velocity of 10mL/min~30mL/min
Be passed through nitrogen 3min~5min in kettle, empty the air in reaction kettle, continue to be passed through nitrogen until air pressure reach 0.1MPa~
0.5MPa；The reaction kettle is high-temperature high-pressure reaction kettle.
9. the preparation method according to any one of claim 2~5, which is characterized in that in the step S4, the hot pressing
Molding uses heat pressing forming device；It is described hot-forming in the process controlled at 120 DEG C~140 DEG C；The hot-forming mistake
Cheng Zhong, single it is hot-forming needed for raw material quality be 0.8g~1g, pressure be the kN of 2 kN~4, the duration be 30s~
40s。
10. system described in any one of a kind of biomass solid clean fuel as described in claim 1 or claim 2~9
Application of the biomass solid clean fuel in burned for energy made from Preparation Method.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110331020A (en) * | 2019-06-28 | 2019-10-15 | 安徽杰沃循环农业发展有限公司 | A kind of preparation method of moisture-proof high-energy biomass granular fuel |
| CN111171889A (en) * | 2019-12-05 | 2020-05-19 | 南京工业大学 | High-concentration organic wastewater and organic solid waste treatment process and system |
| CN111471502A (en) * | 2020-04-08 | 2020-07-31 | 石河子市国力源环保制浆有限公司 | Clean high-value utilization method of straw resources |
| CN115124210A (en) * | 2022-07-26 | 2022-09-30 | 内蒙古大学 | Method for preparing high-carbon low-ash functional carbon material from sludge organic solid waste based on thermokalite hydrolysis coupled acid catalysis hydrothermal carbonization |
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| WO2013187955A1 (en) * | 2012-06-15 | 2013-12-19 | Regents Of The University Of Minnesota | Hydrothermal carbonization of sewage wastes |
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| WO2013187955A1 (en) * | 2012-06-15 | 2013-12-19 | Regents Of The University Of Minnesota | Hydrothermal carbonization of sewage wastes |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110331020A (en) * | 2019-06-28 | 2019-10-15 | 安徽杰沃循环农业发展有限公司 | A kind of preparation method of moisture-proof high-energy biomass granular fuel |
| CN111171889A (en) * | 2019-12-05 | 2020-05-19 | 南京工业大学 | High-concentration organic wastewater and organic solid waste treatment process and system |
| CN111471502A (en) * | 2020-04-08 | 2020-07-31 | 石河子市国力源环保制浆有限公司 | Clean high-value utilization method of straw resources |
| CN115124210A (en) * | 2022-07-26 | 2022-09-30 | 内蒙古大学 | Method for preparing high-carbon low-ash functional carbon material from sludge organic solid waste based on thermokalite hydrolysis coupled acid catalysis hydrothermal carbonization |
| CN115124210B (en) * | 2022-07-26 | 2023-12-22 | 内蒙古大学 | Method for preparing high-carbon low-ash functional carbon material by catalyzing hydrothermal carbonization based on thermal alkaline hydrolysis and acid |
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