CN116312847A - Method for predicting dynamic contamination and slagging trend of biomass ash based on ashing temperature change - Google Patents
Method for predicting dynamic contamination and slagging trend of biomass ash based on ashing temperature change Download PDFInfo
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- 239000002028 Biomass Substances 0.000 title claims abstract description 168
- 238000011109 contamination Methods 0.000 title claims abstract description 90
- 238000004380 ashing Methods 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 68
- 230000008859 change Effects 0.000 title claims abstract description 21
- 238000005245 sintering Methods 0.000 claims abstract description 50
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 33
- 230000008569 process Effects 0.000 claims abstract description 33
- 238000002844 melting Methods 0.000 claims abstract description 31
- 230000008018 melting Effects 0.000 claims abstract description 31
- 239000000155 melt Substances 0.000 claims abstract description 9
- 238000004364 calculation method Methods 0.000 claims description 32
- 239000002893 slag Substances 0.000 claims description 24
- 230000004927 fusion Effects 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 14
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 238000004876 x-ray fluorescence Methods 0.000 claims description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000010079 rubber tapping Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
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- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 9
- 150000001340 alkali metals Chemical class 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000002956 ash Substances 0.000 description 200
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- 238000006243 chemical reaction Methods 0.000 description 7
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- 239000010883 coal ash Substances 0.000 description 6
- 235000005822 corn Nutrition 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- WNQQFQRHFNVNSP-UHFFFAOYSA-N [Ca].[Fe] Chemical compound [Ca].[Fe] WNQQFQRHFNVNSP-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 238000013528 artificial neural network Methods 0.000 description 1
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- 239000003546 flue gas Substances 0.000 description 1
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Classifications
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- G—PHYSICS
- G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
- G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
- G16C20/00—Chemoinformatics, i.e. ICT specially adapted for the handling of physicochemical or structural data of chemical particles, elements, compounds or mixtures
- G16C20/30—Prediction of properties of chemical compounds, compositions or mixtures
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F30/00—Computer-aided design [CAD]
- G06F30/20—Design optimisation, verification or simulation
-
- G—PHYSICS
- G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
- G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
- G16C20/00—Chemoinformatics, i.e. ICT specially adapted for the handling of physicochemical or structural data of chemical particles, elements, compounds or mixtures
- G16C20/10—Analysis or design of chemical reactions, syntheses or processes
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F2119/00—Details relating to the type or aim of the analysis or the optimisation
- G06F2119/08—Thermal analysis or thermal optimisation
Abstract
The invention discloses a biomass ash dynamic contamination slagging trend prediction method based on ashing temperature change, which relates to the technical field of biomass ash contamination slagging prediction and comprises the following steps: determining the sintering rate and sintering characteristic index of biomass ash at different temperatures; determining the melting characteristic temperature and the melting characteristic index of biomass ash at different temperatures; determining stationary phase contamination slagging index and volatile phase contamination slagging index in biomass ashing process at different temperatures; and judging the comprehensive contamination and slagging trend of the biomass ash. The method has the beneficial effects that the method is based on the change rule of the melt characteristic index and the ash sintering rate of the biomass ash at different ashing temperatures, comprehensively considers the distribution and distribution rule of alkali metal components in a stationary phase and a volatile phase in the process of contaminating and slagging the biomass ash, overcomes the defect that the melt characteristic and the sintering characteristic of the biomass ash are ignored in the prior art, and improves the accuracy and the reliability of the prediction result of the dynamic contamination and slagging trend of the biomass ash at different ashing temperatures.
Description
Technical Field
The invention relates to the technical field of biomass contamination slagging prediction, in particular to a biomass ash dynamic contamination slagging trend prediction method based on ashing temperature change.
Background
Biomass thermal conversion technology is currently receiving increasing attention worldwide as a high-efficiency biomass energy utilization way. However, biomass contains a large amount of alkali metal elements such as potassium and sodium, and the coexistence of a large amount of alkali metal elements together with alkaline earth metal elements such as calcium and magnesium and nonmetallic elements such as chlorine and sulfur can lead to the formation of a large amount of alkali metal compounds, and the alkali metal components reduce ash melting points, so that the ash contamination and slagging of biomass ash are main reasons. In view of the current situation of biomass thermal conversion application, the development of the technology is severely restricted by the harm of ash deposition, slag formation and the like caused by the alkali metal problem, and the effective reduction of the pollution and slag formation harm of biomass ash is the actual problem which needs to be solved in the biomass thermal conversion utilization process.
In the process of the contamination and slagging of biomass ash, ash melting and sintering are mutually associated. Sintering refers to the process of pore exclusion and volume shrinkage of soot particles into dense particles of a certain strength at temperatures below their melting temperature. In terms of ash fusion characteristics, biomass ash is a mixture of multiple mineral components, and thus has no fixed melting point, melts only over a range of temperatures, and biomass ash fusion characteristics are often characterized by four characteristic temperatures: deformation Temperature (DT), softening Temperature (ST), hemispherical Temperature (HT) and Flow Temperature (FT). In essence, the melting and sintering characteristics of ash are closely related to not only ash components but also ash temperature, atmosphere, etc., and greatly affect the contamination and slag bonding characteristics of ash. The ashing temperature is taken as a research basis of biomass ash characteristics, and no unified standard exists worldwide at present: the ashing temperature is specified in U.S. ASTM/E870-82 as 600℃and in the European Union SS-ISO540 standard as 550 ℃. At present, relevant standards are not yet developed in China, and the existing research is still carried out by referring to 815+/-10 ℃ specified in the coal quality analysis standard (GB/T212-2008).
In the utilization process of biomass energy, if the pollution and slagging characteristics of biomass ash generated by the biomass energy can be accurately known before the fuel is used, a series of measures can be taken for the biomass to reduce the slagging risk of the biomass. Therefore, whether the tendency of the biomass ash to stain and slag formation can be accurately predicted is important to what measures are taken to inhibit the slag formation. The indexes for judging the pollution and slagging of the coal ash at home and abroad are many, and the common indexes include ash melting point, ash component, ash viscosity and the like of the coal. There is currently no specific standard for evaluating biomass ash for its fouling and slagging. The existing evaluation of the pollution and slagging of the biomass ash generally directly refers to or corrects the pollution and slagging discrimination indexes of the coal ash, such as alkali-acid ratio, silicon-aluminum ratio, alkaline index, iron-calcium ratio and the like. Although the biomass ash components are similar to the coal ash components in kind, because the content difference of each component in the biomass ash components is large, the slag bonding tendency of the biomass ash is judged by simply using the slag bonding index of the coal ash, so that the deviation of the judgment result is large, and serious limitation and inadaptability exist.
For this reason, some scholars propose multi-index discrimination methods based on this, such as a comprehensive discrimination index method, a fuzzy mathematic method, a pattern recognition method, and an artificial neural network method. The method improves the accuracy of the result to a certain extent, but still hardly meets the actual requirement, and has larger deviation, and the main reasons are that the method only usually considers the influence of solid residual ash or molten state components after the thermal conversion of fuel on the pollution and slagging, ignores the influence of the melting temperature, sintering rate and other melting sintering characteristics of ash on the pollution and slagging, ignores the influence of biomass released into flue gas in a gas phase form in the thermal conversion process, deposits alkali metal components in the deposited ash due to various physical or chemical actions, ignores the influence of the dynamic change relation between the volatility of the components and the temperature on the pollution and slagging, and causes the lack of pertinence in the pollution and slagging prediction of biomass ash at different temperatures in the existing method. Therefore, the ash characteristics of the biomass ash and the melting and sintering characteristics of the ash at different temperatures are comprehensively considered, and a more reliable judging method suitable for biomass ash contamination and slagging prediction at different ashing temperatures is explored.
At present, no complete unified standard for biomass ash pollution slagging prediction is available at home and abroad, serious inadaptability exists in the simple follow-up slag bonding index of the coal ash, and the existing slag bonding prediction method generally only considers the influence of residual ash components after fuel thermal conversion on ash slagging, neglects the influence of ash melting temperature, sintering rate and other melting sintering processes on the pollution slagging characteristics of the biomass ash, and neglects the influence of the volatility of alkali metal, chlorine, sulfur and other elements on the temperature change relation. Therefore, on the basis of the previous research, the ash content characteristics and ash fusion sintering characteristics of biomass ash under different thermal conversion conditions are combined, and a pollution and slag bonding prediction model applicable to biomass ash under different temperatures is explored, so that the pollution and slag bonding prediction model is more accurate and effective.
Disclosure of Invention
In order to solve the technical problems, the invention discloses a biomass ash dynamic contamination slagging trend prediction method based on ashing temperature change, which is based on the change rule of melt characteristic index and ash sintering rate of biomass ash at different ashing temperatures, comprehensively considers the distribution and distribution rule of alkali metal components in a stationary phase and a volatile phase in the biomass ash contamination slagging process, and is suitable for biomass ash dynamic contamination slagging prediction methods based on gas-solid two-phase distribution rules at different ashing temperatures.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the biomass ash dynamic contamination slagging trend prediction method based on the ashing temperature change specifically comprises the following steps:
step one, determining the sintering rate and sintering characteristic index of biomass ash at different temperatures;
step two, determining the melting characteristic temperature and the melting characteristic index of biomass ash at different temperatures;
step three, determining stationary phase contamination slagging index and volatile phase contamination slagging index in the biomass ashing process at different temperatures;
and step four, judging the comprehensive contamination and slagging trend of the biomass ash.
Further, the specific process of the first step is as follows:
(1.1) crushing and grinding the biomass raw material air-dried under natural conditions, screening a required biomass particle sample to be used as a biomass powder sample, and putting the biomass powder sample into a sealing bag for standby;
(1.2) weighing a proper amount of prepared biomass powder sample, uniformly paving the biomass powder sample in a crucible, and placing the crucible in a muffle furnace;
(1.3) ashing temperature at 600℃as a reference, denoted as T 600 Heating the muffle furnace to 600 ℃ or a specified temperature, and preserving heat for 2 hours, so as to prepare reference ash or biomass ash at the specified temperature;
(1.4) after the ash preparation is finished, taking out the crucible, cooling to normal temperature and weighing after the furnace temperature is reduced to below 200 ℃;
(1.5) residual Ash obtained at a certain ashing temperature is taken as a stationary phase, a lost part is taken as a volatile phase, the yield of the stationary phase at the ashing temperature is calculated by using the following formula, and the yield is recorded as Ash:
Ash％＝(M 2 -M 1 )/M 0 ×100％(1)
wherein M is 0 Mass of biomass sample, M 1 The quality of the crucible is recorded; m is M 2 Is the total mass of the crucible and the biomass ash;
(1.6) calculating the yield of volatile phase at the specific ashing temperature according to the law of conservation of mass, and recording as Gas, wherein the calculation formula is as follows:
Gas％＝100％-Ash％(2)
(1.7) reversely buckling the crucible in the sieve, tapping the bottom of the crucible, vibrating all the biomass ash samples in the crucible to fall on the sieve, continuously vibrating for 1min, and finally weighing the ash sample net weight on the sieve by using an electronic balance;
(1.8) calculation of the reference temperature at 600 ℃The sintering rate of the biomass ash sample is recorded as ASI a,600 The calculation formula is as follows:
ASI a,600 ＝M 3 /(M 2 -M 1 )(3)
wherein M is 3 Is ash sample net weight;
(1.9) ASI a,600 ASI obtained at a certain ashing temperature as a reference ash sintering rate a,T ASI relative to reference ash sintering rate a,600 The percentage of the biomass ash at the temperature is expressed as D ASI,T The calculation formula is as follows:
D ASI,T ＝ASI a,T /ASI a,600 (4)
in the formula, ASI a,T Is the sintering rate of biomass ash at a certain ashing temperature higher than 600 ℃.
Further, the specific process of the second step is as follows:
(2.1) directly measuring the deformation temperature and hemispherical temperature of the biomass ash prepared at different temperatures by using an intelligent ash melting point measuring instrument;
(2.2) using ash fusion characteristic index to represent the fusion characteristic of biomass ash, and marking as AFI, wherein the calculation formula is as follows:
AFI＝(4DT+HT)/5(5)
wherein DT is the deformation temperature of the biomass ash, and DT is the DT of the biomass ash;
(2.3) calculating an ash fusion characteristic index of the reference ash at 600 ℃;
(2.4) calculating ash fusion characteristic index of the biomass ash obtained at a certain ashing temperature T;
(2.5) calculating the dimensionless percentage of the melt characteristic index of the biomass ash relative to the melt characteristic index of the standard ash at a certain temperature, and recording as D AFI,T The calculation formula is as follows:
D AFI,T ＝AFI a,T /AFI a,600 (6)
in the formula, AFI a,600 Ash fusion characteristic index, AFI, of 600 ℃ reference ash a,600 Is the ash fusion characteristic index of biomass ash at a certain ashing temperature above 600 ℃.
Further, the specific process of the third step is as follows:
(3.1) measuring the chemical composition of the prepared biomass ash at a certain ashing temperature by using an X-ray fluorescence spectrometer, namely, the chemical composition is marked as W x X represents different oxides, including K 2 O、Na 2 O、CaO、MgO、SO 3 、Fe 2 O 3 、SiO 2 、Al 2 O 3 、TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Measuring chlorine content in ash by ion chromatograph, and recording as W Cl ；
(3.2) at a certain temperature, the stationary phase contamination slagging index obtained in the ashing process of the biomass is recorded as R b/a,s,T The calculation formula is as follows:
R b/a,s,T ＝[(W K2O +W Na2O +W CaO +W MgO +W Fe2O3 +W SO3 +W Cl )/(W SiO2 +W Al2O3 +W TiO2 )] s,T ×(T/T 600 )
wherein T is 600 The ashing temperature at which the reference ash was prepared is 600 ℃, and T represents a certain set ashing temperature;
(3.3) calculating the volatile phase contamination slagging index R b/a,g,T The calculation formula is as follows:
R b/a,g,T ＝R b/a,s,T ×(Gas％/Ash％) (7)
in the above, R b/a,s,T Contamination slagging index for stationary phase;
(3.4) calculating the final ash integrated contamination slagging index of the biomass based on the change of the ashing temperature, and marking as R b/a,T The calculation formula is as follows:
R b/a,T ＝D ASI,T ×D AFI,T ×R b/a,s,T ×R b/a,g,T (8)。
further, the specific process of the fourth step is as follows:
(4.1) calculating stationary phase contamination slagging index and volatile phase contamination slagging index of a reference ash, respectively designated R, with respect to a certain biomass, using ash prepared at an ashing temperature of 600 ℃ as the reference ash b/a,s,600 And R is b/a,g,600 Then calculate the synthetic contamination slagging finger of the reference ashThe number is recorded as R b/a,600 ；
(4.2) calculating the D of the Biomass ash at a certain temperature ASI,T 、D AFI,T 、R b/a,s,T And R is b/a,g,T And from this, the integrated fouling slagging index R of the biomass ash at this temperature is calculated b/a,T ；
(4.3) according to R at a certain temperature b/a,T The size of the calculated result is combined with the calculated result of the comprehensive contamination slagging index of the reference ash, the contamination slagging tendency of the biomass ash at the temperature is divided into three grades of slight, moderate and serious, and the discrimination limits are as follows:
when R is b/a,T ≤1/2R b/a,600 When the slag is slightly polluted, the slag is formed;
when 1/2R b/a,600 ＜R b/a,T ≤2R b/a,600 When in use, the slag is formed for moderate contamination;
when R is b/a,T ＞2R b/a,600 In the process, slag formation is caused by serious contamination.
The invention has the advantages that,
1) The invention provides a calculation method of stationary phase contamination slagging index and volatile phase contamination slagging index in biomass ash process at different temperatures based on melting and sintering characteristic change rules of biomass ash at different temperatures, fully considers distribution rules of sulfur, chlorine and alkali metal components in stationary phase and volatile phase in contamination slagging process, and provides a biomass ash dynamic contamination slagging prediction method based on gas-solid two-phase distribution rules at different ash temperatures.
2) The method overcomes the defect that the traditional prediction research on the pollution and slagging trend of the biomass ash ignores the melting characteristic and sintering characteristic of the biomass ash, fully considers the influence of the dynamic change relation between the volatile phase and the temperature on pollution and slagging, and improves the accuracy and reliability of the prediction result of the dynamic pollution and slagging trend of the biomass ash at different ashing temperatures.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a biomass ash dynamic contamination slagging prediction method based on a gas-solid two-phase distribution rule at different ashing temperatures, which can provide scientific guidance for accurately predicting contamination slagging trend of biomass ash at different ashing temperatures and has important significance for taking measures for reasonably and effectively inhibiting contamination slagging of biomass ash in actual production process based on the variation rule of melting and sintering characteristics of biomass ash at different ashing temperatures and the collection and distribution rule of sulfur, chlorine and alkali metal components in a stationary phase and a volatile phase in the contamination slagging process of biomass ash.
A biomass ash dynamic contamination slagging trend prediction method based on ashing temperature change comprises the following specific processes:
(1) And determining the sintering rate and sintering characteristic index of the biomass ash at different temperatures. Specifically:
(1.1) crushing and grinding the biomass raw material air-dried under natural conditions, screening a required biomass particle sample by a 100-mesh sieve (the particle size is less than or equal to 0.154 mm) to obtain a biomass powder sample, and putting the biomass powder sample into a sealing bag for standby;
(1.2) weighing a proper amount of the prepared biomass powder sample by using an electronic balance and uniformly paving the biomass powder sample in a crucible, wherein the mass of the biomass sample is recorded as M 0 The crucible mass is recorded as M 1 And placed in a muffle furnace;
(1.3) ashing temperature, defined as T, was measured based on 600℃as a reference according to the standard of ASTM-E1755-01, method of analysis of biomass industry 600 Heating the muffle furnace to 600 ℃ or a specified temperature, and preserving heat for 2 hours, so as to prepare reference ash or biomass ash at the specified temperature;
(1.4) after the ash preparation is completed, after the furnace temperature is reduced to below 200 ℃, taking out the crucible, cooling to normal temperature, weighing, and recording the total mass of the crucible and the biomass ash as M 2 ；
(1.5) residual Ash obtained at a certain ashing temperature was used as a stationary phase, the lost part was used as a volatile phase, and the yield of the stationary phase at the ashing temperature was calculated by using the following formula and recorded as ash%:
Ash％＝(M 2 -M 1 )/M 0 ×100％(1)
wherein M is 0 Mass of biomass sample, M 1 The quality of the crucible is recorded; m is M 2 Is the total mass of the crucible and the biomass ash;
(1.6) according to the law of conservation of mass, the yield of volatile phase at this particular ashing temperature was calculated as Gas%:
Gas％＝100％-Ash％(2)
(1.7) reversely buckling the crucible in a 100-mesh sieve, tapping the bottom of the crucible, vibrating all the biomass ash samples in the crucible to fall on the sieve, continuously vibrating for 1min, and finally weighing the ash sample net weight on the sieve by an electronic balance, wherein the net weight is recorded as M 3 ；
(1.8) finally, calculating the sintering rate of the biomass ash sample at the reference temperature of 600 ℃ by using the following formula, and marking the sintering rate as ASI a,600 ：
ASI a,600 ＝M 3 /(M 2 -M 1 )(3)
Wherein M is 3 Is ash sample net weight;
(1.9) ASI a,600 ASI obtained at a certain ashing temperature as a reference ash sintering rate a,T ASI relative to reference ash sintering rate a,600 The percentage of the biomass ash at the temperature is expressed as D ASI,T ：
D ASI,T ＝ASI a,T /ASI a,600 (4)
In the formula, ASI a,T Is the sintering rate of biomass ash at a certain ashing temperature higher than 600 ℃.
(2) The melting characteristic temperature and the melting characteristic index of the biomass ash at different temperatures are determined. In particular, the method comprises the steps of,
(2.1) directly measuring the deformation temperature and hemispherical temperature of the biomass ash prepared at different temperatures by using an intelligent ash melting point measuring instrument;
(2.2) using ash fusion characteristic index to represent the fusion characteristic of biomass ash, and marking as AFI, wherein the calculation formula is as follows:
AFI＝(4DT+HT)/5(5)
wherein DT is the deformation temperature of the biomass ash, and DT is the DT of the biomass ash;
(2.3) calculating the ash fusion characteristic index of the reference ash at 600 ℃ and recording as AFI a,600 ；
(2.4) calculating an ash fusion characteristic index of the obtained biomass ash at a certain ashing temperature T, and recording the ash fusion characteristic index as AFI a,T ；
(2.5) calculating the dimensionless percentage of the melt characteristic index of the biomass ash relative to the melt characteristic index of the standard ash at a certain temperature, and recording as D AFI,T The calculation formula is as follows:
D AFI,T ＝AFI a,T /AFI a,600 (6)
in the formula, AFI a,600 Ash fusion characteristic index, AFI, of 600 ℃ reference ash a,600 Is the ash fusion characteristic index of biomass ash at a certain ashing temperature above 600 ℃.
(3) And determining stationary phase contamination slagging index and volatile phase contamination slagging index in the biomass ashing process at different temperatures. In particular, the method comprises the steps of,
(3.1) measuring chemical composition of the obtained biomass ash at a certain ashing temperature by using an X-ray fluorescence spectrometer (XRF), wherein the content of oxide is recorded as W x X represents different oxides, including K 2 O、Na 2 O、CaO、MgO、SO 3 、Fe 2 O 3 、SiO 2 、Al 2 O 3 、TiO 2 Etc.; measuring chlorine content in ash by Ion Chromatograph (IC), and recording as W Cl ；
(3.2) referring to the alkali-acid ratio of the slagging prediction index commonly used for judging the slagging tendency of coal ash pollution, fully considering the synergistic effect of components such as sulfur, chlorine and the like in the biomass ash pollution slagging process, providing the stationary phase pollution slagging index obtained in the biomass ash incineration process at a certain temperature, and marking as R b/a,s,T The calculation formula is as follows:
R b/a,s,T ＝[(W K2O +W Na2O +W CaO +W MgO +W Fe2O3 +W SO3 +W Cl )/(W SiO2 +W Al2O3 +W TiO2 )] s,T ×(T/T 600 )
wherein R is b/a,s,T The index of fouling and slagging of a biomass ash stationary phase at a certain ashing temperature is shown, the subscript s of the index shows the stationary phase, T 600 The ashing temperature at which the reference ash was prepared is 600 ℃, and T represents a certain set ashing temperature;
(3.3) calculating a volatile phase contamination slagging index R by taking the ratio of the volatile phase yield to the stationary phase yield as a volatile phase acting factor b/a,g,T The calculation formula is as follows:
R b/a,g,T ＝R b/a,s,T ×(Gas％/Ash％)(7)
in the above formula, R b/a,g,T The index of contamination and slagging of the volatile phase of biomass ash at a certain ashing temperature is shown, the subscript g of the index shows the volatile phase, R b/a,s,T Is the stationary phase contamination slagging index, T 600 The ashing temperature at which the reference ash was prepared is 600 ℃, and T represents a certain set ashing temperature;
(3.4) comprehensively considering the sintering characteristic index, the melting characteristic index, the stationary phase contamination slagging index and the volatile phase contamination slagging index of the biomass ash, calculating the final biomass ash comprehensive contamination slagging index based on the change of the ashing temperature, and marking as R b/a,T The calculation formula is as follows:
R b/a,T ＝D ASI,T ×D AFI,T ×R b/a,s,T ×R b/a,g,T (8)。
(4) And judging the comprehensive contamination and slagging trend of the biomass ash. In particular, the method comprises the steps of,
(4.1) calculating stationary phase contamination slagging index and volatile phase contamination slagging index of a reference ash, respectively designated R, with respect to a certain biomass, using ash prepared at an ashing temperature of 600 ℃ as the reference ash b/a,s,600 And R is b/a,g,600 Then calculate the integrated contamination slagging index of the reference ash, which is marked as R b/a,600 ；
(4.2) according to the above calculation formula,calculating D of biomass ash at a certain temperature ASI,T 、D AFI,T 、R b/a,s,T And R is b/a,g,T And from this, the integrated fouling slagging index R of the biomass ash at this temperature is calculated b/a,T ；
(4.3) according to R at a certain temperature b/a,T The size of the calculated result is combined with the calculated result of the comprehensive contamination slagging index of the reference ash, the contamination slagging tendency of the biomass ash at the temperature is divided into three grades of slight, moderate and serious, and the discrimination limits are as follows:
when R is b/a,T ≤1/2R b/a,600 When the slag is slightly polluted, the slag is formed;
when 1/2R b/a,600 ＜R b/a,T ≤2R b/a,600 When in use, the slag is formed for moderate contamination;
when R is b/a,T ＞2R b/a,600 In the process, slag formation is caused by serious contamination.
Examples
Taking a great amount of cornstalk biomass existing in northeast area as an example, the pollution and slagging trend of cornstalks at the ashing temperature of 400 ℃ and 800 ℃ is predicted and analyzed, and the method specifically comprises the following steps:
(1) crushing and grinding the air-dried cornstalks, screening a required powder sample through a 100-mesh sieve (the particle size is less than or equal to 0.154 mm), and preparing cornstalk ash at the ashing temperature of 400 ℃, 600 ℃ and 800 ℃ respectively;
(2) according to the method, the yields of the stationary phase and the volatile phase in the corn stalk ashing process at different temperatures are calculated, wherein the yields are respectively expressed by Ash% and Gas%, and the calculated results are shown in table 1;
TABLE 1 yields of stationary and volatile phases in cornstalk ashing at different temperatures
(3) According to the above method, the sintering rate and sintering characteristic index of the prepared cornstalk powder sample at 400deg.C, 600deg.C and 800deg.C are measured, and ASI is used for the sintering rate test results at 400deg.C, 600deg.C and 800deg.C a,400 、ASI a,600 And ASI a,800 Representing the ash sample prepared at 400 ℃ and 800 ℃ relative to the reference ash sintering rate ASI a,600 The sintering characteristic index calculation results of (C) are respectively D ASI,400 And D ASI,800 And (3) representing.
Here, the sintering characteristic index of the ash based on the ash at 600℃is represented by the formula D ASI,T ＝ASI a,T /ASI a,600 Calculated, the sintering characteristic index of the reference ash at 600 ℃ is equal to 1. If ASI a,T > 1, the ash sample sintering degree is weaker at the temperature; if ASI a,T A value of < 1 indicates that the ash sample is strongly sintered at this temperature. Normally, the higher the ashing temperature, the higher the degree of sintering of the same biomass, under the same other conditions such as ashing time and atmosphere. The measurement results of the sintering rate and the sintering characteristic index of the cornstalk ash obtained at 400 ℃, 600 ℃ and 800 ℃ are shown in Table 2.
TABLE 2 determination of the sintering Rate and sintering Property index of cornstalk ash at different temperatures
(4) Measuring Deformation Temperature (DT) and Hemispherical Temperature (HT) of cornstalk ash at 400 deg.C, 600 deg.C and 800 deg.C by using intelligent ash melting point tester, calculating melt characteristic indexes of ash at different temperatures, respectively using AFI a,400 、AFI a,600 And AFI a,800 Representing, simultaneously calculating dimensionless index D of melting characteristic index of cornstalk ash at 400 ℃ and 800 ℃ relative to standard ash at 600 DEG C AFI,T Respectively using D AFI,400 And D AFI,T And (3) representing.
Here, the ash melting characteristic dimensionless index is calculated by the formula D based on 600 ℃ ash AFI,T ＝AFI a,T /AFI a,600 Calculated, thus 600 ℃ reference ash D AFI,600 Equal to 1. If D AFI,T More than 1 indicates that the ash sample prepared at the temperature has higher melting degree; if D AFI,T A value of < 1 indicates that the ash sample is melted to a low degree at this temperature. Normally, ashing time,When other conditions such as atmosphere are the same, the higher the ashing temperature, the higher the degree of melting of the obtained biomass ash for the same biomass. The melting characteristic index and the non-dimensional melting characteristic index D of the cornstalk ash are obtained at 400 ℃, 600 ℃ and 800 DEG C AFI,T The measurement results are shown in Table 3.
TABLE 3 determination of sintering Rate and sintering Property index of cornstalk Ash at 400 ℃, 600 ℃ and 800 DEG C
(5) The chemical composition of the cornstalk ash was measured at 400 c, 600 c and 800 c using an X-ray fluorescence spectrometer (XRF), and the content of elemental chlorine in each ash was measured using an Ion Chromatograph (IC), and the test results are shown in table 4.
Table 4 chemical composition test results (%)
| Ashing temperature | SiO 2 | Na 2 O | MgO | Al 2 O 3 | SO 3 | K 2 O | CaO | Fe 2 O 3 | TiO 2 | Cl |
| 400℃ | 24.64 | 12.16 | 3.29 | 1.83 | 1.23 | 31.67 | 6.42 | 0.51 | 0.12 | 8.39 |
| 600℃ | 29.65 | 5.75 | 4.23 | 2.66 | 4.92 | 26.11 | 5.29 | 0.67 | 0.05 | 7.26 |
| 800℃ | 32.31 | 4.06 | 6.64 | 2.12 | 5.43 | 24.24 | 6.87 | 0.46 | 0.09 | 5.15 |
(6) Calculating stationary phase contamination slagging index R b/a,s,T 。
According to the chemical composition test result of ash sample, calculating stationary phase contamination slagging index in the process of ashing cornstalk at 400 ℃, 600 ℃ and 800 ℃ according to the above formula, respectively using R b/a,s,400 、R b/a,s,600 And R is b/a,s,800 The calculation results are shown in table 5.
TABLE 5 calculation of stationary phase contamination slagging index during corn stalk ashing at different temperatures
| Ashing temperature | Stationary phase contamination slagging index R b/a,s,T |
| 400℃ | 1.60 |
| 600℃ | 1.68 |
| 800℃ | 2.04 |
(7) Calculating the contamination slagging index R of volatile phase b/a,g,T 。
According to R b/a,g,T ＝R b/a,s,T X (Gas%/Ash%) calculation formula, calculating volatile phase contamination slagging index in corn stalk ashing process at 400 ℃, 600 ℃ and 800 ℃ respectively using R b/a,g,400 、R b/a,g,600 And R is b/a,g,800 The calculation results are shown in table 6.
TABLE 6 calculation of volatile phase contamination slagging index during corn stalk ashing at different temperatures
| Ashing temperature | R b/a,s,T | Ash％ | Gas％ | Volatile phase contamination slagging index R b/a,g,T |
| 400℃ | 1.60 | 17.9％ | 82.1％ | 7.34 |
| 600℃ | 1.68 | 15.9％ | 84.1％ | 8.89 |
| 800℃ | 2.04 | 13.7％ | 86.3％ | 12.85 |
(8) According to calculated D of biomass ash ASI,T 、D AFI,T And R is b/a,s,T Calculating the comprehensive contamination slagging index of the cornstalk ash at 400 ℃, 600 ℃ and 800 ℃ by R respectively b/a,400 、R b/a,600 And R is b/a,800 The calculation results are shown in table 7.
TABLE 7 preparation of cornstalk ash D at different temperatures ASI，T 、D AFI，T 、R b/a，s，T And R is b/a，T Summarizing calculation results
| Ashing temperature | D ASI,T | D AFI,T | R b/a,s,T | R b/a,g,T | Index R of integrated contamination and slag formation b/a,T |
| 400℃ | 0.68 | 0.97 | 1.60 | 7.34 | 7.75 |
| 600℃ | 1.00 | 1.00 | 1.68 | 8.89 | 14.94 |
| 800℃ | 1.42 | 1.18 | 2.04 | 12.85 | 43.92 |
(9) Predicting the comprehensive contamination slagging tendency of corn stalk ash:
the corn stalk ash prepared at the ashing temperature of 600 ℃ is used as reference ash, and the comprehensive contamination slagging index R of the reference ash b/a,600 =14.94; when the ashing temperature is 400 ℃, the comprehensive contamination slagging index R b/a,400 =7.75, at 1/2R b/a,600 ＜R b/a,T ≤2R b/a,600 Therefore, the comprehensive contamination slagging tendency of the cornstalk ash at 400 ℃ can be predicted to be moderate; when the ashing temperature is 800 ℃, the comprehensive contamination slagging index R b/a,800 =43.92, at R b/a,T ＞2R b/a,600 Therefore, the comprehensive contamination slagging tendency of the cornstalk ash at 800 ℃ can be predicted to be serious. The prediction result is consistent with the relevant experimental result, and the reliability and the accuracy of the prediction method are verified.
It should be understood that the above description is not intended to limit the invention to the particular embodiments disclosed, but to limit the invention to the particular embodiments disclosed, and that the invention is not limited to the particular embodiments disclosed, but is intended to cover modifications, adaptations, additions and alternatives falling within the spirit and scope of the invention.
Claims (5)
1. The biomass ash dynamic contamination slagging trend prediction method based on the ashing temperature change is characterized by comprising the following steps of:
step one, determining the sintering rate and sintering characteristic index of biomass ash at different temperatures;
step two, determining the melting characteristic temperature and the melting characteristic index of biomass ash at different temperatures;
step three, determining stationary phase contamination slagging index and volatile phase contamination slagging index in the biomass ashing process at different temperatures;
and step four, judging the comprehensive contamination and slagging trend of the biomass ash.
2. The method for predicting the dynamic fouling and slagging trend of biomass ash based on the change of ashing temperature according to claim 1, wherein the specific process of the first step is as follows:
(1.1) crushing and grinding the biomass raw material air-dried under natural conditions, screening a required biomass particle sample to be used as a biomass powder sample, and putting the biomass powder sample into a sealing bag for standby;
(1.2) weighing a proper amount of prepared biomass powder sample, uniformly paving the biomass powder sample in a crucible, and placing the crucible in a muffle furnace;
(1.3) ashing temperature at 600℃as a reference, denoted as T 600 Heating the muffle furnace to 600 ℃ or a specified temperature, and preserving heat for 2 hours, so as to prepare reference ash or biomass ash at the specified temperature;
(1.4) after the ash preparation is finished, taking out the crucible, cooling to normal temperature and weighing after the furnace temperature is reduced to below 200 ℃;
(1.5) residual Ash obtained at a certain ashing temperature is taken as a stationary phase, a lost part is taken as a volatile phase, the yield of the stationary phase at the ashing temperature is calculated by using the following formula, and the yield is recorded as Ash:
Ash％＝(M 2 -M 1 )/M 0 ×100％
wherein M is 0 Mass of biomass sample, M 1 The quality of the crucible is recorded; m is M 2 Is a crucible andthe total mass of biomass ash;
(1.6) calculating the yield of volatile phase at the specific ashing temperature according to the law of conservation of mass, and recording as Gas, wherein the calculation formula is as follows:
Gas％＝100％-Ash％
(1.7) reversely buckling the crucible in the sieve, tapping the bottom of the crucible, vibrating all the biomass ash samples in the crucible to fall on the sieve, continuously vibrating for 1min, and finally weighing the ash sample net weight on the sieve by using an electronic balance;
(1.8) calculating the sintering rate of the biomass ash sample at the reference temperature of 600 ℃, and recording as ASI a,600 The calculation formula is as follows:
ASI a,600 ＝M 3 /(M 2 -M 1 )
wherein M is 3 Is ash sample net weight;
(1.9) ASI a,600 ASI obtained at a certain ashing temperature as a reference ash sintering rate a,T ASI relative to reference ash sintering rate a,600 The percentage of the biomass ash at the temperature is expressed as D ASI,T The calculation formula is as follows:
D ASI,T ＝ASI a,T /ASI a,600
in the formula, ASI a,T Is the sintering rate of biomass ash at a certain ashing temperature higher than 600 ℃.
3. The method for predicting the dynamic contamination slagging trend of biomass ash based on the change of the ashing temperature according to claim 1, wherein the specific process of the second step is as follows:
(2.1) directly measuring the deformation temperature and hemispherical temperature of the biomass ash prepared at different temperatures by using an intelligent ash melting point measuring instrument;
(2.2) using ash fusion characteristic index to represent the fusion characteristic of biomass ash, and marking as AFI, wherein the calculation formula is as follows:
AFI＝(4DT+HT)/5
wherein DT is the deformation temperature of the biomass ash, and DT is the DT of the biomass ash;
(2.3) calculating an ash fusion characteristic index of the reference ash at 600 ℃;
(2.4) calculating ash fusion characteristic index of the biomass ash obtained at a certain ashing temperature T;
(2.5) calculating the dimensionless percentage of the melt characteristic index of the biomass ash relative to the melt characteristic index of the standard ash at a certain temperature, and recording as D AFI,T The calculation formula is as follows:
D AFI,T ＝AFI a,T /AFI a,600
in the formula, AFI a,600 Ash fusion characteristic index, AFI, of 600 ℃ reference ash a,600 Is the ash fusion characteristic index of biomass ash at a certain ashing temperature above 600 ℃.
4. The method for predicting the dynamic fouling and slagging trend of biomass ash based on the change of ashing temperature according to claim 1, wherein the specific process of the third step is as follows:
(3.1) measuring the chemical composition of the prepared biomass ash at a certain ashing temperature by using an X-ray fluorescence spectrometer, namely, the chemical composition is marked as W x X represents different oxides, including K 2 O、Na 2 O、CaO、MgO、SO 3 、Fe 2 O 3 、SiO 2 、Al 2 O 3 、TiO 2 The method comprises the steps of carrying out a first treatment on the surface of the Measuring chlorine content in ash by ion chromatograph, and recording as W Cl ；
(3.2) at a certain temperature, the stationary phase contamination slagging index obtained in the ashing process of the biomass is recorded as R b/a,s,T The calculation formula is as follows:
R b/a,s,T ＝[(W K2O +W Na2O +W CaO +W MgO +W Fe2O3 +W SO3 +W Cl )/(W SiO2 +W Al2O3 +W TiO2 )] s,T ×(T/T 600 )
wherein T is 600 The ashing temperature at which the reference ash was prepared is 600 ℃, and T represents a certain set ashing temperature;
(3.3) calculating the volatile phase contamination slagging index R b/a,g,T The calculation formula is as follows:
R b/a,g,T ＝R b/a,s,T ×(Gas％/Ash％)
in the above, R b/a,s,T Contamination slagging index for stationary phase;
(3.4) calculating the final ash integrated contamination slagging index of the biomass based on the change of the ashing temperature, and marking as R b/a,T The calculation formula is as follows:
R b/a,T ＝D ASI,T ×D AFI,T ×R b/a,s,T ×R b/a,g,T 。
5. the method for predicting the dynamic contamination slagging trend of biomass ash based on the change of the ashing temperature according to claim 1, wherein the specific process of the fourth step is as follows:
(4.1) calculating stationary phase contamination slagging index and volatile phase contamination slagging index of a reference ash, respectively designated R, with respect to a certain biomass, using ash prepared at an ashing temperature of 600 ℃ as the reference ash b/a,s,600 And R is b/a,g,600 Then calculate the integrated contamination slagging index of the reference ash, which is marked as R b/a,600 ；
(4.2) calculating the D of the Biomass ash at a certain temperature ASI,T 、D AFI,T 、R b/a,s,T And R is b/a,g,T And from this, the integrated fouling slagging index R of the biomass ash at this temperature is calculated b/a,T ；
(4.3) according to R at a certain temperature b/a,T The size of the calculated result is combined with the calculated result of the comprehensive contamination slagging index of the reference ash, the contamination slagging tendency of the biomass ash at the temperature is divided into three grades of slight, moderate and serious, and the discrimination limits are as follows:
when R is b/a,T ≤1/2R b/a,600 When the slag is slightly polluted, the slag is formed;
when 1/2R b/a,600 ＜R b/a,T ≤2R b/a,600 When in use, the slag is formed for moderate contamination;
when R is b/a,T ＞2R b/a,600 In the process, slag formation is caused by serious contamination.
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