CN112480986B - Coke inhibitor and preparation method and use method thereof - Google Patents
Coke inhibitor and preparation method and use method thereof Download PDFInfo
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- CN112480986B CN112480986B CN202011342790.3A CN202011342790A CN112480986B CN 112480986 B CN112480986 B CN 112480986B CN 202011342790 A CN202011342790 A CN 202011342790A CN 112480986 B CN112480986 B CN 112480986B
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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
- C10L5/42—Solid fuels essentially based on materials of non-mineral origin on animal substances or products obtained therefrom, e.g. manure
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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
- C10L10/00—Use of additives to fuels or fires for particular purposes
- C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
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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
- C10L9/00—Treating solid fuels to improve their combustion
- C10L9/10—Treating solid fuels to improve their combustion by using additives
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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
Abstract
The application discloses a coking inhibitor, a preparation method and a use method thereof, which comprise coking inhibition chemicals; the scorch inhibiting chemical comprises component I; the component I contains sulfur element and calcium element. The invention can effectively fix and convert potassium sulfate and potassium chloride which are easy to coke and slag, so that the potassium sulfate and the potassium chloride are converted into loose, fragile and difficult to coke and slag, the coking and slag bonding process can be effectively blocked, and the coking and slag bonding condition of the heating surface of the boiler can be eliminated or relieved.
Description
Technical Field
The application relates to a coke inhibitor, a preparation method and a use method thereof, and belongs to the technical field of biomass power generation boilers.
Background
The biomass energy is one of renewable clean energy, and the biomass incineration power generation is an effective way for recycling waste. The biomass boiler is one of power generation equipment commonly used for biological incineration power generation. At present, the conventional coal-fired power generation boiler is used as a reference for the device and the process flow of the biological power generation boiler. Due to the great difference between the properties and components of the biofuel and the coal, the components and properties of ash produced by the combustion of the biofuel are completely different. Generally, the main components of the fly ash after biomass combustion are potassium chloride and potassium sulfate, the fly ash can cause serious ash deposition, coking and slagging, and transition products such as sulfur dioxide, hydrogen chloride, potassium oxide and the like can cause corrosion on a heating surface to influence the normal operation of a boiler. Especially, the biological material taking livestock and poultry breeding waste as the main fuel, such as the mixture of chicken manure and rice husk, has high content of potassium sulfate and potassium chloride in the burnt ash, and the original fuel has extremely high humidity, so that the fly ash generated under the environment has higher viscosity, is easier to coke and slag on a heating surface, seriously reduces the heat transfer efficiency of the boiler, shortens the operation period of the boiler, and greatly limits the efficiency improvement of the boiler. In addition, the deposited ash is easy to solidify and coke, and is not easy to fall off on a steel pipe of the heat exchanger, so that great workload and potential safety hazard are brought to subsequent shutdown cleaning, and the economic benefit of boiler power generation is seriously influenced. Therefore, the problem of coking and slagging of the boiler heat exchanger is solved, and the method has important significance for improving the efficiency of the livestock and poultry breeding waste power generation boiler, prolonging the service life of the boiler and improving the economic benefit of the power generation boiler.
Disclosure of Invention
Against the above background, the present invention is to solve the following technical problems, including but not limited to: the technical problem of coking and slagging of the heating surface of the biomass power generation boiler is solved; large area required by drying or baking the biomass fuel in the sun and heat consumption. The coke inhibitor provided by the application comprises a coke inhibiting chemical product; the scorch inhibiting chemical comprises component I; the component I contains sulfur element and calcium element. The invention can effectively fix and convert potassium sulfate and potassium chloride which are easy to coke and slag, so that the potassium sulfate and the potassium chloride are converted into loose, fragile and difficult to coke and slag, the coking and slag bonding process can be effectively blocked, and the coking and slag bonding condition of the heating surface of the boiler can be eliminated or relieved.
According to a first aspect of the present application, there is provided a scorch retarder comprising a scorch retarding chemical; the scorch inhibiting chemical comprises component I;
the component I contains sulfur element and calcium element.
Optionally, the calcium element in the component I is at least one of calcium oxide, calcium hydroxide and calcium salt;
the sulfur element in the component I is from a salt compound containing the sulfur element.
Optionally, the salt compound containing the sulfur element is selected from at least one of calcium sulfate, calcium sulfite and calcium sulfide.
Optionally, the calcium salt is selected from at least one of calcium sulfate, calcium sulfite, calcium sulfide, calcium chloride, calcium carbonate, and calcium oxalate.
Optionally, the calcium and sulfur elements are derived from sulfur, calcium element-containing inorganic salts or mixed inorganic salts.
Optionally, the inorganic salt or mixed inorganic salt containing elemental sulfur or calcium comprises a mixture of a sulfate salt and a calcium salt.
Optionally, the inorganic salt or mixed inorganic salt containing sulfur and calcium elements comprises one or more of calcium sulfate, calcium sulfite and calcium sulfide.
Optionally, in the component I, the molar ratio of the calcium element to the sulfur element is (5-1): 1.
optionally, the scorch inhibiting chemical further comprises component II and component III;
the component II contains magnesium;
the component III contains phosphorus element.
Optionally, the component II comprises at least one of magnesium salt, magnesium oxide and magnesium hydroxide.
Optionally, in the coking resistant chemical product, the molar ratio of the magnesium element, the phosphorus element and the sulfur element is 0.01-31.5: 21-60: 16 to 64.
Optionally, in the coking resistant chemical, the upper limit of the molar ratio of the magnesium element, the phosphorus element, and the sulfur element is independently selected from 9: 54: 64. 10: 60: 20, the lower limit is independently selected from 2: 28: 42. 9: 54: 64. 10: 60: 20.
optionally, the phosphorus element in the component III is one or more of red phosphorus, phosphorus pentoxide, calcium phosphate and magnesium phosphate.
Optionally, the calcium phosphate salt is selected from at least one of basic calcium phosphate and magnesium calcium phosphate.
Optionally, the magnesium calcium hydrogen phosphate has the formula shown in formula I:
CaxMgyHz(PO4)nformula I
In the formula I, x, y, z, n, 1 to 18, 1 to 2, 2 to 14.
Optionally, the coke inhibitor further comprises quartz sand.
Optionally, the mass content of the quartz sand in the coke inhibitor is 6.5-39 wt%.
Optionally, the upper limit of the mass content of the quartz sand in the coke inhibitor is independently selected from 39wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt%, 10 wt%, and the lower limit is independently selected from 6.5 wt%, 30 wt%, 25 wt%, 20 wt%, 15 wt%, 10 wt%.
Optionally, the coking resistant chemical has a particle size of less than 0.8 mm; the particle size of the quartz sand is less than 1 mm.
Optionally, the scorch inhibiting chemical comprises the following components:
component 1: the inorganic salt or mixed inorganic salt containing sulfur and calcium elements is included, and the inorganic salt or mixed inorganic salt containing sulfur and calcium elements comprises a mixture of sulfate and calcium salt; further, one or more of calcium sulfate, calcium sulfite and calcium sulfide are included; in the component 1, the molar component weight of calcium and sulfur are 16-64 parts;
and (2) component: comprises calcium salt or calcium oxide or sulfide, further comprises one or more of calcium hydroxide, calcium oxide, calcium chloride, calcium carbonate, calcium oxalate and calcium sulfide; in the component 2, the molar component amount of calcium is 0-63 parts;
and (3) component: including magnesium salts or oxides or hydroxides of magnesium; further, one or more of magnesium oxide, magnesium hydroxide and magnesium sulfate are included; in the component 3, the molar component amount of the magnesium element is 0-20 parts;
and (4) component: comprises a phosphorus-containing compound, further comprises one or more of red phosphorus, phosphorus pentoxide, calcium phosphate and magnesium phosphate; in the component 4, the molar component amount of the phosphorus element is 21-60 parts.
In the process of burning biomass with ash elements of chlorine, potassium and sulfur as main element components, the chlorine, potassium and sulfur elements are volatilized and combined to form fly ash aerosol with potassium chloride and potassium sulfate as main components, the potassium sulfate has high viscosity and is easy to adhere to convection tube bundles, superheaters, coal-saving gas and air preheaters in the flowing process of flue gas, the adhered potassium sulfate is easy to adsorb potassium chloride particles with low melting points and easy to sublimate on the surface of the potassium sulfate particles, and more potassium sulfate and potassium chloride are adhered, adsorbed, accumulated and agglomerated repeatedly in such a way along with the evolution of time.
The most main factor causing the coking problem is potassium sulfate with high adhesiveness in fly ash, and in order to block a series of chain coking reactions caused by the potassium sulfate, a scheme of fly ash component conversion is adopted, namely, fly ash mainly containing potassium sulfate and potassium chloride is converted into fly ash components difficult to coke in real time after the blocking reaction of a coking inhibitor, and the accumulated ash is discharged from the bottom of a heat exchanger furnace body in time by a mechanical method under the action of gravity.
The main reaction mechanisms include:
1. and (3) fixation and transformation of potassium sulfate:
CaSO4(s)+K2SO4(s)+H2O(g)＝K2Ca(SO4)2·H2O(s)
because of the constant oxygen supply in the furnace, the calcium sulfate in the reaction can be replaced by calcium sulfite or calcium sulfide. Because calcium sulfite or calcium sulfide can be easily converted into calcium sulfate by burning in air.
Likewise, the calcium sulfate in this reaction has the same properties as calcium sulfate with crystal water (including gypsum or plaster of Paris), and therefore calcium sulfate can also be replaced with calcium sulfate with crystal water (e.g., gypsum or plaster of Paris).
The final product of the reaction is potassium gypsum with crystal water, and the potassium gypsum can be dehydrated and decomposed at high temperature to generate potassium sulfate under normal conditions, and the generated potassium sulfate can still cause coking. However, in the embodiment of the present invention, since the biomass used has a large moisture content, for example, the mixture of chicken manure and chaff has a moisture content of more than 40%, in this case, when the combustion is performed, the hearth is filled with a large amount of water vapor, and the humidity of the hearth reaches RH 100%. Under the condition of water vapor with high concentration, according to the chemical reaction equilibrium principle, the reaction can only be carried out in a forward reaction mode but not in a reverse reaction mode, and therefore the purpose of fixing potassium sulfate is achieved.
2. Coating and fixing potassium chloride;
10Ca(OH)2(s)+3P2O5(g)＝2Ca5(PO4)3(OH)(s)+9H2O(g)
CaO(s)+MgO(s)+P2O5(g)+H2O(g)＝CaxMgyHz(PO4)n(s)
Ca3(PO4)2(s)+MgO(s)+H2O(g)＝CaxMgyHz(PO4)n(s)
in reaction 2, the product is magnesium calcium hydrogen phosphate, and the values of x, y, z and n are determined by the relative quantitative ratio of elements such as CaMgH in the feed2(PO4)2，Ca4MgH2(PO4)4，Ca4MgH2(PO4)4，Ca18Mg2H2(PO4)14，Ca7MgH2(PO4)6，Ca10Mg2H2(PO4)8And the like.
Under the conditions of oxygen atmosphere and high temperature, the product generated in the reaction 1 is basic calcium phosphate, wherein Ca (OH)2Can be replaced by calcium hydroxide, calcium oxide, calcium chloride, calcium carbonate, calcium oxalate or calcium sulfide; p2O5Can be replaced by red phosphorus, phosphorus pentoxide or calcium phosphate;
under the conditions of oxygen atmosphere and high temperature, CaO in the reaction 2 can be replaced by calcium hydroxide, calcium chloride, calcium carbonate, calcium oxalate or calcium sulfide; p2O5Can be replaced by red phosphorus, phosphorus pentoxide or calcium phosphate; MgO can be replaced by magnesium hydroxide, magnesium sulfate, and magnesium phosphate.
The basic calcium phosphate and the magnesium calcium hydrogen phosphate have the functions of adsorbing and coating potassium chloride aerosol generated by a hearth, and direct contact between potassium chloride and a heating surface is reduced, so that a steel pipe on the heating surface is prevented from coking and corrosion.
After the coking resistance treatment, the components in the fly ash are changed from a potassium sulfate and potassium chloride coking mixture into a mixture consisting of potassium chloride, magnesium calcium hydrogen phosphate, basic calcium phosphate and potassium gypsum which are coated inside, the fly ash of the mixture can not agglomerate and form slag under high temperature and high humidity, and can not be solidified and coked into hard blocks but form a sand-gravel-shaped flowable mixture, so that the coking on a steel pipe on a heating surface is avoided, and the coking problem of a boiler can be solved only by collecting and emptying the fly ash at the bottom of a boiler body in time by utilizing the action of gravity or negative pressure pumping.
The research of the invention shows that because the highest temperature of the biomass hearth is between 800-1200 ℃, the quartz sand does not participate in the chemical reaction in the whole ash forming process, but because the potassium sulfate in the fly ash is not ready to react with the coke inhibitor at the beginning of formation, the particles of the fly ash easily form crystal nuclei on the heating surface and grow continuously in the initial coking stage, and the fused potassium chloride particles are easy to deposit on the potassium sulfate on the surface of the heating surface to further form ash, so that the coke inhibiting effect is delayed inevitably because the potassium sulfate is not effectively blocked in the initial coking, therefore, the quartz sand has a large effect at the moment, the quartz sand with small particle size can provide nucleation sites for the potassium sulfate fly ash to guide the potassium sulfate to grow and crystallize on the surface, thereby further reducing the coking of the potassium chloride on the heating surface and delaying the initial coking and slagging of the heating surface, meanwhile, the quartz sand has good fluidity and is easier to settle, and the coking and slagging conditions can be further relieved by emptying the accumulated dust at the bottom in time. It is to be noted that since the effect of blocking coking is greater in the initial stage of coking but significantly reduced in the latter stage of coking, the amount of the quartz sand to be charged is larger in the initial stage of biomass incineration, but the amount of the quartz sand to be charged in the latter stage can be reduced as appropriate, and generally, the amount to be charged in the latter stage is 1/2 of the initial amount to be charged with respect to the weight content of the coke inhibitor. Because the initial time granule of quartz sand is just bigger, and weight is heavy, if direct and biomass fuel mixed use, then cause its most part to be subsided promptly in burning furnace, it can't play the effect effectively at the superheater position, has weakened whole coke-blocking efficiency. Therefore, the invention further optimizes the separate use of the coking-resistant chemicals and the quartz sand, namely, optionally, the coking-resistant chemicals and the biomass fuel are mixed and burned, and the quartz sand is periodically injected into the high-temperature superheater part. Because the content difference of the silicon dioxide contained in the ash of the biomass is larger, the using amount of the quartz sand can be properly reduced if the content of the silicon dioxide in the ash of the biomass is larger; if the content of silicon dioxide in the biomass ash is extremely high (more than 60 wt%), quartz sand can be omitted.
Optionally, the scorch inhibiting chemical comprises the following components:
and (2) component A: comprises one or more of calcium sulfate, calcium sulfite and calcium sulfide; in the component A, the molar component amount of calcium element is 16-64 parts;
and (B) component: including basic calcium phosphate [ Ca ]5(PO4)3(OH)]And magnesium calcium hydrogen phosphate [ Ca ]xMgyHz(PO4)n]One or more of (a); in the component B, the molar component amount of the phosphorus element is 21-60 parts.
After the coke inhibitor is added, the components of the final deposited ash have small acting force due to the huge difference between crystal structures, and the components can not be effectively agglomerated. To further verify, we found that the settled ash formed finally did not agglomerate and remained as a flowing gravel after burning in humid air at 1200 ℃ for 6 hours, which also indicates that the forces between the ash product compounds were small.
According to the second aspect of the application, the application of at least one of the coking inhibitor and the coking inhibitor prepared by the method in a biomass power generation boiler is also provided.
Optionally, the biomass in the biomass power generation boiler is at least one of livestock and poultry breeding waste, pine wood powder and bamboo powder.
Optionally, the livestock and poultry breeding waste is selected from at least one of chicken manure and rice husk.
The livestock and poultry breeding waste biomass selected in the embodiment of the invention has high sulfur content (the sulfur element accounts for 1.11 wt% of the dry biomass), and the produced ash has higher viscosity and higher coking resistance difficulty.
According to a third aspect of the application, a use method of the biomass power generation boiler coke inhibitor is further provided, and the use method comprises at least one of the following methods:
the method comprises the following steps: feeding the coking-resistant chemicals into an incineration hearth of a biomass power generation boiler for incineration;
the second method comprises the following steps: feeding the coking-resistant chemicals into the boiler from at least one of the positions of the openings on the two sides of the horizontal flue at the outlet of the separator of the biomass power generation boiler, the openings on the two sides outside the high-temperature superheater area, the openings on the two sides outside the low-temperature superheater area, the openings on the two sides outside the economizer area or the openings on the two sides outside the air preheater area;
the scorch retarding chemicals are selected from at least one of the scorch retarders described above.
Optionally, the method of use comprises at least one of:
the method I comprises the following steps: feeding the coking-resistant chemicals and the quartz sand into an incineration hearth of a biomass power generation boiler for incineration;
method II: feeding the coking-resistant chemicals and the quartz sand into the boiler from at least one of the openings on two sides of a horizontal flue at the outlet of a separator of the biomass power generation boiler, the openings on two sides outside a high-temperature superheater area, the openings on two sides outside a low-temperature superheater area, the openings on two sides outside an economizer area or the openings on two sides outside an air preheater area;
method III: and (3) feeding the quartz sand in the coke inhibitor into the boiler from at least one of the openings on two sides of a horizontal flue at the outlet of a separator of the biomass power generation boiler, the openings on two sides outside a high-temperature superheater area, the openings on two sides outside a low-temperature superheater area, the openings on two sides outside an economizer area or the openings on two sides outside an air preheater area, and feeding the coke-inhibiting chemical in the coke inhibitor into an incineration hearth of the biomass power generation boiler for incineration.
Optionally, in the method I, the method II and the method III, the amount of the added quartz sand is decreased day by day with the operation cycle of the biomass power generation boiler, and the amount of the added quartz sand is decreased daily to 1.4 to 1.8 wt% of the weight of the quartz sand in the previous day.
Preferably, the amount of the quartz sand in the coke inhibitor is gradually decreased along with the operation period of the boiler, and the amount of the quartz sand is decreased to 1/2 of the content of the last quartz sand relative to the content of the first quartz sand in the coke inhibitor.
Regarding the selection of the position of injecting the coke inhibitor into the boiler, the horizontal flue at the outlet of the separator of the biomass power generation boiler, a high-temperature superheater area, a low-temperature superheater area, an economizer area or an opening of an air preheater area can be optionally injected. Because the areas are communicated and the flow direction of the flue is the horizontal flue at the outlet of the separator, the high-temperature superheater area, the low-temperature superheater area, the economizer area and the air preheater area, the selection of the upstream area for spraying in the flow of the flue is more favorable, the reaction is more sufficient and the effect of blocking coking is better. And the effect is better when the water is sprayed into the areas simultaneously.
According to a final aspect of the present application, there is provided a method of generating power for a biomass power generating boiler, the method comprising at least one of:
method a 1: mixing the coking-resistant chemicals and the biomass fuel, and then sending the mixture into an incineration hearth of a biomass power generation boiler for incineration;
method a 2: feeding the coking-resistant chemicals from at least one of the positions of the openings on two sides of the horizontal flue at the outlet of the separator of the biomass power generation boiler, the openings on two sides outside the high-temperature superheater area, the openings on two sides outside the low-temperature superheater area, the openings on two sides outside the economizer area or the openings on two sides outside the air preheater area, and feeding the biomass fuel into the incineration hearth of the biomass power generation boiler for incineration;
the scorch retarding chemicals are selected from at least one of the scorch retarders described above.
Optionally, the power generation method comprises at least one of the following methods:
method c 1: mixing the coking-resistant chemicals, the quartz sand and the biomass fuel, and then sending the mixture into an incineration hearth of a biomass power generation boiler for incineration;
method c 2: feeding quartz sand in a coking inhibitor from at least one of openings on two sides of a horizontal flue at an outlet of a separator of the biomass power generation boiler, openings on two sides outside a high-temperature superheater area, openings on two sides outside a low-temperature superheater area, openings on two sides outside an economizer area or openings on two sides outside an air preheater area, and feeding coking chemicals and biomass fuel in the coking inhibitor into an incineration hearth of the biomass power generation boiler for incineration;
method c 3: and feeding the coking-resistant chemicals and the quartz sand from at least one of the openings on two sides of a horizontal flue at the outlet of a separator of the biomass power generation boiler, the openings on two sides outside a high-temperature superheater area, the openings on two sides outside a low-temperature superheater area, the openings on two sides outside an economizer area or the openings on two sides outside an air preheater area, and feeding the biomass fuel into an incineration hearth of the biomass power generation boiler for incineration.
Optionally, the coke inhibitor is 0.125-1.5% of the mass of the biomass fuel.
Optionally, the upper limit of the mass of the coke inhibitor is independently selected from 1.5%, 1.2%, 1.0%, 0.8%, 0.6%, 0.4%, 0.2%, and the lower limit is independently selected from 0.125%, 1.2%, 1.0%, 0.8%, 0.6%, 0.4%, 0.2%.
Optionally, the water content of the biomass fuel is 30.5-49.2 wt%.
The coke blocking position of the invention mainly aims at the position of the heating surface of each heat exchanger in the hearth of the superheater, and the specific position is shown in figure 3.
The beneficial effects that this application can produce include:
1. the invention can effectively fix and convert potassium sulfate and potassium chloride which are easy to coke and slag, so that the potassium sulfate and the potassium chloride are converted into loose, fragile and difficult to coke and slag, the coking and slag bonding process can be effectively blocked, and the coking and slag bonding condition of the heating surface of the boiler can be eliminated or relieved;
2. the boiler coke inhibitor can effectively fix and convert potassium sulfate and potassium chloride which are easy to coke and slag, so the boiler coke inhibitor has universality in a certain range, is suitable for biomass boilers with ash deposition components of potassium sulfate and potassium chloride, and can realize effective coke inhibition by adjusting the proportion of each component in the coke inhibitor according to the specific composition of each biomass ash deposition component.
3. Can effectively absorb the transitional gas product SO in the combustion process2And Cl2And HCl reduces the corrosion to the heating surface of the boiler.
4. In order to relieve the coking and slagging condition of a boiler and improve the calorific value of fuel, the biomass fuel is dried and aired before being burnt. However, the biomass burned every day is huge, and the processes of drying and airing require huge fields and consume a large amount of heat energy, and the drying and airing of livestock and poultry wastes such as chicken manure cause serious environmental pollution and do not have the condition of dry fuel, so that most biomass fuels are burned after being dried and do not have practical economic conditions. Under the condition, the coke inhibitor provided by the invention can effectively block the fly ash from coking slag in a high-humidity environment, and the trouble is well solved.
5. Partial water is absorbed, and the effective heat value of the fuel is improved.
6. The invention can obviously reduce the problems of slag bonding and ash deposition of the biomass boiler, reduce the corrosion of the metal pipe wall, improve the heat conduction of the heating surface, increase the heat efficiency and improve the energy efficiency of the boiler.
7. The livestock and poultry breeding waste biomass power generation boiler coke inhibitor has the advantages of simple use method, low cost and wide application prospect.
Drawings
FIG. 1 is an XRD pattern of soot deposition on a superheater in example 1;
FIG. 2 is an XRD pattern of soot deposition at the bottom of the superheater in example 3;
FIG. 3 is a schematic structural diagram of a biomass power generation boiler in the present application, and in FIG. 3, "high province" -high temperature economizer; "Low-province" -a low-temperature economizer; "over-high" -a high temperature superheater; "low pass" -low temperature superheater; the economizer comprises a low-temperature economizer and a high-temperature economizer.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
All raw materials used in the present invention except those specifically mentioned are commercially available at home.
Phase analysis: analysis was performed using an X-ray powder diffractometer (XRD, Rigaku, Miniflex 600).
Example 1 (comparative example)
The biomass fuel adopted in the embodiment is a mixture containing wet chicken manure and rice husk (wherein the rice husk content is 70 wt%, and the chicken manure content is 30 wt%), the water content is 30.5-49.2%, and the average water content is 40.1 wt% (the water content of the biomass input every day is different due to the influence of climate transportation factors, so the range is represented); the biomass fuel is applied to a chicken manure circulating fluidized bed power generation boiler for incineration power generation, and long-time operation monitoring shows that the period of continuous normal operation of a boiler system is 30 days, the situation of ash deposition and coking on a superheater is severe, the ash deposition, coking and slagging are blocked, flag-shaped slagging ash deposition is arranged on the windward side, and the biomass fuel is hard and difficult to clean. The main components of the deposited ash of the superheater are KCl, potassium sulfate and chlorinated basic calcium phosphate, the deposited ash deposited at the bottom of the hearth is less, and the deposited ash accounts for 12 wt% of the weight of all the coked deposited ash.
Performing phase analysis on the ash deposition on the superheater (figure 1), wherein the main components of the ash deposition on the superheater comprise KCl, potassium sulfate and basic calcium phosphate chloride (Ca)505(PO4)3.014Cl0.595(OH)1.67)。
Example 2
The difference between the embodiment and the embodiment 1 is that the biomass fuel is added with a coking inhibitor, the coking inhibitor comprises coking resistant chemicals and quartz sand, and the particle size of the quartz sand is 0.2-0.8 mm; the components of the coke-resistant chemicals are as follows: calcium sulfate; the coking resistant chemical in the embodiment accounts for 0.25 percent of the mass proportion of the raw biomass fuel, and the weight fraction of the quartz sand relative to the raw biomass fuel is 0.05 to 0.025 percent. Pulverizing the coking-resistant chemicals in the proportion to the maximum particle size of less than 0.8mm, uniformly mixing the pulverized coking-resistant chemicals with biomass fuel, and feeding the mixture into a power generation boiler for combustion; after the boiler starts to normally operate, quartz sand is sprayed into the boiler periodically (once every 1h, the time length of each spraying is 10min, the amount of the quartz sand sprayed into each spraying inlet is the same until all the quartz sand planned to be sprayed is sprayed out) from the openings on two sides of a horizontal flue at the outlet of a separator of the biomass boiler, the openings on two sides of the outer part of a high-temperature superheater area, the openings on two sides of the outer part of a low-temperature superheater area, the openings on two sides of an economizer area and the openings on two sides of the outer part of an air preheater area (shown in figure 3), the amount of the sprayed quartz sand is gradually reduced day by day along with the operation period of the boiler, the amount of the sprayed quartz sand is gradually reduced from 0.05 wt% of the initial biomass dosage to 0.025 wt% of the last time day, and the average gradually reduced amount is 1.8% of the quartz sand dosage of the previous day.
The coke inhibitor provided by the embodiment is applied to a chicken manure circulating fluidized bed boiler, and long-time operation monitoring shows that the continuous normal operation period of a boiler system is 38 days, the ash deposition and coking conditions on a superheater are obviously improved, and the corrosion problem of a heat exchange surface is also obviously relieved. The self-settled ash at the bottom of the superheater is obviously increased, the weight of the bottom ash is 42 wt% of the weight of all the coking ash (the sum of the coking ash deposition of the superheater and the ash deposition settled at the bottom of the superheater), the main components of the bottom ash deposition mainly comprise potassium gypsum, basic calcium phosphate, magnesium calcium hydrogen phosphate and KCl, the ash deposition property of the bottom ash deposition is expressed as loose sand gravel, the superheater and the ash are not coked and slagged, and the superheater and the ash deposition easily flow under the action of gravity or negative pressure.
Example 3:
the difference between the embodiment and the embodiment 1 is that the biomass fuel is added with a coking inhibitor, the coking inhibitor comprises coking resistant chemicals and quartz sand, the weight of the quartz sand is 26-13 wt% of the whole coking inhibitor (the content of the quartz sand in the coking inhibitor is dynamically changed every day), and the particle size of the quartz sand is 0.2-0.8 mm; the anti-coking chemical comprises the following components in molar weight ratio:
calcium sulfate: 16 parts of a mixture;
calcium oxide: 63 parts of a mixture;
magnesium phosphate: 21 parts (based on the molar amount of phosphorus);
quartz sand: 26 wt% to 13 wt% (mass fraction relative to the whole coke inhibitor)
Pulverizing the coking-resistant chemicals in the proportion to the maximum particle size of less than 0.8mm, uniformly mixing the pulverized chemicals with quartz sand and biomass fuel, and feeding the mixture into an incinerator chamber of a power generation boiler for combustion; the amount of the quartz sand in the coke inhibitor is gradually reduced day by day along with the operation period of the boiler, and is gradually reduced from 26 wt% of the initial content to 13 wt% of the last time day by day (the average daily decrement is 1.6% of the quartz sand dosage on the previous day). The coke inhibitor of the embodiment accounts for 0.45 percent of the mass proportion of the original biomass fuel.
The coke inhibitor provided by the embodiment is applied to a chicken manure circulating fluidized bed boiler, and long-time operation monitoring shows that the period of continuous normal operation of a boiler system is 42 days, the situation of ash deposition and coking on a superheater is obviously improved, and the problem of corrosion of a heat exchange surface is also obviously relieved. The self-settling deposition at the bottom of the superheater is obviously increased, the weight of the deposition at the bottom is 52 wt% of the weight of all coking deposition, the main components of the deposition at the bottom are potassium gypsum, basic calcium phosphate, magnesium calcium hydrogen phosphate and KCl, the deposition property of the deposition at the bottom is expressed as loose sand gravel, no coking and slagging are realized, and the deposition easily flows under the action of gravity or negative pressure.
The bottom ash sample was analyzed for phase (FIG. 2), and the analysis showed that potassium gypsum [ K ] is the main component of the ash2Ca(SO4)2·H2O]Basic calcium phosphate [ Ca ]5(PO4)3(OH)]Magnesium calcium hydrogen phosphate [ Ca ]18Mg2H2(PO4)14]And KCl.
Example 4
The embodiment is different from the embodiment 1 in that a coking inhibitor is added into the biomass fuel, the coking inhibitor comprises coking resistant chemicals and quartz sand, the weight of the quartz sand is 39-19.5 wt% of the total coking inhibitor, and the particle size of the quartz sand is 0.1-0.6 mm; the anti-coking chemical comprises the following components in molar weight ratio:
calcium sulfate: 64 parts;
magnesium hydroxide: 9 parts of (1);
calcium phosphate: 27 parts (in terms of the molar amount of phosphorus);
quartz sand: 39wt% to 19.5 wt% (mass fraction relative to the whole coke inhibitor)
After the coking-resistant chemical product with the proportion is crushed to the maximum grain size of less than 0.8mm, the coking-resistant chemical product is mixed with quartz sand, and the mixture is sprayed into a boiler periodically (sprayed into the boiler once every 1h, the time length of each spraying is 10min, the amount of the coking-resistant agent sprayed into each spraying opening is the same until all the planned sprayed coking-resistant agent is sprayed) from the openings on the two sides of a horizontal flue at the outlet of a separator of the biomass boiler, the openings on the two sides of the high-temperature superheater area, the openings on the two sides of the low-temperature superheater area, the openings on the two sides of the economizer area and the openings on the two sides of the air preheater area, wherein the amount of the quartz sand in the coking-resistant agent is gradually decreased day by day along with the operation period of the boiler, and is gradually decreased from 39wt% of the initial content to 19.5 wt% of the last time (the average gradual decrease is 1.4% of the quartz sand dosage of the previous day). The coke inhibitor of the embodiment accounts for 0.125 percent of the mass proportion of the raw biomass fuel.
The coke inhibitor provided by the embodiment is applied to a chicken manure circulating fluidized bed boiler, and long-time operation monitoring shows that the period of continuous normal operation of a boiler system is 48 days, the situation of dust deposition and coking on a superheater is obviously improved, and the problem of corrosion of a heat exchange surface is also obviously relieved. The self-settling deposition at the bottom of the superheater is obviously increased, the weight of the deposition at the bottom is 63 wt% relative to the weight of all coking deposition, the main components of the deposition at the bottom are potassium gypsum, basic calcium phosphate, magnesium calcium hydrogen phosphate and KCl, the deposition property of the deposition at the bottom is expressed as loose sand gravel, no coking and slagging are realized, and the deposition easily flows under the action of gravity or negative pressure.
Example 5
The embodiment is different from the embodiment 1 in that a coking inhibitor is added into the biomass fuel, the coking inhibitor comprises coking resistant chemicals and quartz sand, the weight of the quartz sand is 13-6.5 wt% of the total coking inhibitor, and the particle size of the quartz sand is 0.4-1 mm; the anti-coking chemical comprises the following components in molar weight ratio:
calcium sulfate: 20 parts of (1);
magnesium sulfate: 20 parts of (1);
calcium phosphate: 60 parts (based on the molar amount of phosphorus);
quartz sand: 13 wt% to 6.5 wt% (mass fraction relative to the whole coke inhibitor)
Crushing the coking-resistant chemicals in the proportion to the maximum particle size of less than 0.8mm, uniformly mixing the crushed coking-resistant chemicals with quartz sand and biomass fuel, and feeding the mixture into a power generation boiler for combustion; the amount of the quartz sand in the coke inhibitor is gradually reduced along with the operation period of the boiler, and is gradually reduced from 13 wt% of the initial content to 6.5 wt% of the last time day by day (the average daily decrement is 1.4% of the quartz sand dosage on the previous day). The coke inhibitor of the embodiment accounts for 1.5 percent of the mass proportion of the original biomass fuel.
The coke inhibitor provided by the embodiment is applied to a chicken manure circulating fluidized bed boiler, and long-time operation monitoring shows that the period of continuous normal operation of a boiler system is 40 days, the situation of dust deposition and coking on a superheater is obviously improved, and the problem of corrosion of a heat exchange surface is also obviously relieved. The self-settling deposition at the bottom of the superheater is obviously increased, the weight of the deposition at the bottom is 46 wt% of the weight of all coking deposition, the main components of the deposition at the bottom are potassium gypsum, basic calcium phosphate, magnesium calcium hydrogen phosphate and KCl, the deposition property of the deposition at the bottom is expressed as loose sand gravel, no coking and slagging are realized, and the deposition easily flows under the action of gravity or negative pressure.
Example 6
In the embodiment, pine wood powder is used as biomass fuel, a firing chemical reaction in a hearth is simulated in a tubular furnace, before firing, the pine wood powder and a coke inhibitor are uniformly mixed, the mass fraction of the coke inhibitor relative to the pine wood powder is 5 wt%, and the molar components of the coke inhibitor are as follows:
calcium sulfate: 42 parts of (A);
calcium oxalate: 42 parts of (A);
magnesium oxide: 2 parts of (1);
P2O 5: 14 parts of (1);
quartz sand: 5 wt% (mass fraction relative to the entire coke inhibitor);
after pine wood powder and a coke inhibitor are uniformly mixed, 1g of mixture is flatly paved in a quartz boat and then placed in a tube furnace for burning, moisture-containing air is continuously introduced into the tube furnace, and the burning procedure is as follows: heating to 800 ℃ from room temperature for 80min, and keeping at 800 ℃ for 2 hours; the burned ash content is tested and analyzed by a powder diffractometer, the main components of the burned ash content comprise potassium gypsum, basic calcium phosphate, magnesium calcium hydrogen phosphate and KCl, no silicate component is detected, and the ash content is loose gravel.
Example 7
The difference between the embodiment and the embodiment 5 is that the biomass fuel is bamboo powder, the mass fraction of the coke inhibitor relative to the bamboo powder is 5%, and the molar components of the coke inhibitor are as follows:
calcium sulfate: 42 parts of (A);
calcium carbonate: 42 parts of (A);
magnesium oxide: 2 parts of (1);
P2O5: 28 parts (based on the molar amount of phosphorus);
quartz sand: 5 wt% (mass fraction relative to the entire coke inhibitor);
the grain diameter of the quartz sand grains is less than 0.8 mm; the particle size of the coke inhibitor is less than 0.2 mm;
the burned ash content is tested and analyzed by a powder diffractometer, the main components of the burned ash content comprise potassium gypsum, basic calcium phosphate, magnesium calcium hydrogen phosphate and KCl, no silicate component is detected, and the ash content is loose gravel.
Example 8
The difference between the embodiment and the embodiment 1 is that the biomass fuel is added with the anti-coking chemicals, and the components of the anti-coking chemicals are as follows: calcium sulfate; the coke-inhibiting chemicals of this example account for 0.25% of the raw biomass fuel mass. The coking-resistant chemicals in the proportion are crushed to the maximum particle size of less than 0.8mm, and then are uniformly mixed with the biomass fuel and are sent into a power generation boiler for combustion.
The coke inhibitor provided by the embodiment is applied to a chicken manure circulating fluidized bed boiler, and long-time operation monitoring shows that the continuous normal operation period of a boiler system is 35 days, the ash deposition and coking conditions on a superheater are improved, and the corrosion problem of a heat exchange surface is relieved. The self-settled ash at the bottom of the superheater is increased, the weight of the bottom ash is 35 wt% of the weight of all the coking ash (the sum of the coking ash of the superheater and the ash settled at the bottom of the superheater), the bottom ash mainly comprises the ash mainly comprising potassium gypsum, basic calcium phosphate, magnesium calcium hydrogen phosphate and KCl, and the ash is loose and gravel, does not coke and is slagged, and is easy to flow under the action of gravity or negative pressure.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (21)
1. The application of the coking inhibitor in the biomass power generation boiler is characterized in that the coking inhibitor comprises coking inhibition chemicals; the scorch inhibiting chemical comprises component I;
the component I contains sulfur element and calcium element;
the fly ash in the biomass power generation boiler comprises potassium sulfate;
the water content of the biomass used in the biomass power generation boiler is 30.5-49.2 wt%, so that a hearth is filled with a large amount of water vapor to form potassium gypsum with a loose structure;
the chemical formula of the potassium gypsum is shown as formula i:
K2Ca(SO4)2•H2and O is represented by the formula i.
2. The use according to claim 1, wherein the calcium element in the component I is at least one of calcium oxide, calcium hydroxide and calcium salt;
the sulfur element in the component I is from a salt compound containing the sulfur element.
3. The use according to claim 2, wherein the salt compound containing elemental sulfur is selected from at least one of calcium sulfate, calcium sulfite, and calcium sulfide.
4. Use according to claim 2, wherein the calcium salt is selected from at least one of calcium sulphate, calcium sulphite, calcium sulphide, calcium chloride, calcium carbonate, calcium oxalate.
5. The use according to claim 2, wherein in the component I, the molar ratio of the calcium element to the sulfur element is (5-1): 1.
6. the use of claim 1, wherein the scorch inhibiting chemical further comprises component II and component III;
the component II contains magnesium;
the component III contains phosphorus;
the fly ash in the biomass power generation boiler also comprises potassium chloride.
7. The use according to claim 6, wherein the magnesium element in the component II is at least one of magnesium salt, magnesium oxide and magnesium hydroxide;
the phosphorus element in the component III is at least one of red phosphorus, phosphorus pentoxide, calcium phosphate and magnesium phosphate.
8. The use according to claim 6, wherein the molar ratio of the magnesium element, the phosphorus element and the sulfur element in the coking resistant chemical product is 0.01-31.5: 21-60: 16 to 64.
9. Use according to claim 7, wherein the calcium phosphate salt is selected from at least one of calcium basic phosphate and magnesium calcium phosphate.
10. The use according to claim 9, wherein the magnesium calcium hydrogen phosphate has the formula I:
CaxMgyHz(PO4) nformula I
In the formula I, x, y, z, n = (1-18): 1-2): 2 (2-14).
11. The use of any one of claims 1 to 10, wherein the scorch inhibitor further comprises silica sand.
12. The use of claim 11, wherein the mass content of the quartz sand in the coke inhibitor is 6.5-39 wt%.
13. The use of claim 11, wherein the anti-coking chemical has a particle size of less than 0.8 mm; the particle size of the quartz sand is less than 1 mm.
14. The application of claim 1, wherein the biomass in the biomass power generation boiler is at least one of livestock and poultry breeding waste, pine wood powder and bamboo powder.
15. The use of claim 14, wherein the livestock and poultry breeding waste is selected from at least one of chicken manure and rice husk.
16. The use of claim 12, wherein the method of using the scorch inhibitor comprises:
and (3) feeding the coking-resistant chemicals into an incineration hearth of a biomass power generation boiler for incineration.
17. The use of claim 16, wherein the method of using the scorch inhibitor comprises:
and (3) feeding the coking-resistant chemicals and the quartz sand into an incineration hearth of the biomass power generation boiler for incineration.
18. The use of claim 17, wherein the amount of added quartz sand decreases day by day with the operating cycle of the biomass power generation boiler, and the amount of added quartz sand decreases day by day to be 1.4-1.8 wt% of the weight of the added quartz sand on the previous day.
19. The use of claim 12, wherein the method of power generation of the coke inhibitor in a biomass power generation boiler comprises at least one of:
method a 1: mixing the coking-resistant chemicals and the biomass fuel, and then sending the mixture into an incineration hearth of a biomass power generation boiler for incineration;
method a 2: and feeding the coking-resistant chemicals from at least one of the positions of the openings on two sides of the horizontal flue at the outlet of the separator of the biomass power generation boiler, the openings on two sides outside the high-temperature superheater area, the openings on two sides outside the low-temperature superheater area, the openings on two sides outside the economizer area or the openings on two sides outside the air preheater area, and feeding the biomass fuel into an incineration hearth of the biomass power generation boiler for incineration.
20. Use according to claim 19, wherein the power generation method comprises at least one of the following methods:
method c 1: mixing the coking-resistant chemicals, the quartz sand and the biomass fuel, and then sending the mixture into an incineration hearth of a biomass power generation boiler for incineration;
method c 2: feeding quartz sand in a coking inhibitor from at least one of openings on two sides of a horizontal flue at an outlet of a separator of the biomass power generation boiler, openings on two sides outside a high-temperature superheater area, openings on two sides outside a low-temperature superheater area, openings on two sides outside an economizer area or openings on two sides outside an air preheater area, and feeding coking chemicals and biomass fuel in the coking inhibitor into an incineration hearth of the biomass power generation boiler for incineration;
method c 3: and feeding the coking-resistant chemicals and the quartz sand from at least one of the openings on two sides of a horizontal flue at the outlet of a separator of the biomass power generation boiler, the openings on two sides outside a high-temperature superheater area, the openings on two sides outside a low-temperature superheater area, the openings on two sides outside an economizer area or the openings on two sides outside an air preheater area, and feeding the biomass fuel into an incineration hearth of the biomass power generation boiler for incineration.
21. The use of claim 20, wherein the coke inhibitor is 0.125-1.5% of the mass of the biomass fuel.
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