CN106833801B - Fe-Ti-Tb ternary composite coal-saving sulfur-fixing decoking additive and preparation method and application thereof - Google Patents

Fe-Ti-Tb ternary composite coal-saving sulfur-fixing decoking additive and preparation method and application thereof Download PDF

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CN106833801B
CN106833801B CN201710098644.2A CN201710098644A CN106833801B CN 106833801 B CN106833801 B CN 106833801B CN 201710098644 A CN201710098644 A CN 201710098644A CN 106833801 B CN106833801 B CN 106833801B
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fixing
ternary composite
sulfur
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coal
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CN106833801A (en
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胡大为
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Guangzhou Fenfang Environmental Protection Technology Co ltd
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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
    • 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
    • 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
    • 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
    • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
    • C10L2230/08—Inhibitors
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/14—Injection, e.g. in a reactor or a fuel stream during fuel production
    • C10L2290/141—Injection, e.g. in a reactor or a fuel stream during fuel production of additive or catalyst

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

Abstract

The invention relates to a preparation method of a Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive, which comprises the following steps: (1) preparation of FeCl2Adding tetrabutyl titanate and terbium salt ethanol solution into the ethanol solution, and uniformly mixing; (2) adding alkali liquor, and aging for more than 24 h; (3) dropping stoichiometric hydrogen peroxide under the protection of nitrogen atmosphere, and keeping the temperature at 60-70 ℃ for more than 1 h; (4) separating out precipitate by using a magnet; (5) after vacuum drying and vacuum calcining, the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive is prepared. Also relates to a Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive prepared by the method and application thereof. The invention has the advantages of simple material selection, convenient preparation, comprehensive performance of energy conservation, sulfur fixation, emission reduction and coking/decoking prevention, and belongs to the technical field of coal additives.

Description

Fe-Ti-Tb ternary composite coal-saving sulfur-fixing decoking additive and preparation method and application thereof
Technical Field
The invention relates to a coal-fired additive technology, in particular to a preparation method of a Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive, relates to the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive prepared by the preparation method, and also relates to application of the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive.
Background
In recent years, the price of coal is continuously rising, and the energy conservation and emission reduction become the most important factor of the current enterprises due to the influence of factors such as further improvement of national emission requirements of coal-fired enterprises. In terms of the current energy-saving and emission-reducing measures of coal-fired enterprises, the conventional means of improving equipment, recovering waste heat and the like are limited by capital investment, equipment improvement allowance and the like, and the received effect is general. Therefore, the demand for new coal-saving additives is gradually increased, and as a new coal-saving agent, the novel coal-saving additive should have: the comprehensive performance of energy conservation, sulfur fixation, emission reduction and coking/decoking prevention is realized, so that the wide applicability of the product is ensured. At present, most of coal-saving agents sold on the market are traditional combustion-supporting coal-saving agents, and have certain effects on coal-fired occasions with low combustion efficiency and low coal burnout rate, but the coal-saving agents cannot obtain satisfactory effects on application occasions such as large-scale power station boilers, coal water slurry furnaces, novel dry-process rotary kiln cement and the like, so that the research on novel multifunctional composite coal-saving additives has important social and economic values.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention aims to: provides a preparation method of a Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive which realizes the comprehensive performance of energy conservation, sulfur fixation, emission reduction and coking/decoking prevention.
The second object of the present invention is: provides the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive which realizes the comprehensive performance of energy conservation, sulfur fixation, emission reduction and coking/decoking prevention.
A third object of the invention is: provides the application of the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive which realizes the comprehensive performance of energy conservation, sulfur fixation, emission reduction and coking/decoking prevention.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation method of the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive comprises the following steps: (1) preparation of FeCl2Adding tetrabutyl titanate and terbium salt ethanol solution into the ethanol solution, and uniformly mixing; (2) adding alkali liquor, and aging for more than 24 h; (3) dropping stoichiometric hydrogen peroxide under the protection of nitrogen atmosphere, and keeping the temperature at 60-70 ℃ for more than 1 h; (4) separating out precipitate by using a magnet; (5) after vacuum drying and vacuum calcining, the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive is prepared. Wherein FeCl2The solute of the ethanol solution is FeCl2The solvent is ethanol; the solute of the terbium salt ethanol solution is terbium salt, and the solvent is ethanol.
Preferably, in the terbium salt ethanol solution in the step (1), the terbium salt is TbCl3、TbF3、TbF4One or two of them.
Preferably, in step (2), the alkali solution added to the mixed solution is KOH ethanol solution or NaOH ethanol solution. Wherein, the solute of the KOH ethanol solution or the NaOH ethanol solution is KOH or NaOH, and the solvent is ethanol.
Preferably, in step (1), FeCl2The concentration of the ethanol solution is 1-2 mol/L, the concentration of the terbium salt ethanol solution is 0.1-0.2 mol/L, and the concentration of the alkali liquor in the step (2) is 10 mol/L.
Preferably, in step (5), the vacuum drying condition is vacuum drying at 75-80 ℃ and the vacuum calcination condition is vacuum calcination at 500 ℃.
The Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive is prepared by adopting a preparation method of the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive.
Preferably, the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive is a powdery material.
The Fe-Ti-Tb ternary composite coal-saving sulfur-fixing decoking additive is used as a coal-saving sulfur-fixing decoking additive for coal.
In summary, the present invention has the following advantages:
the materials are simple to obtain, and the preparation is convenient; in the final product, the Fe-Ti composite material mainly plays a role in improving the effect of fixing sulfur in ash in coal and the melting temperature of coke slag, and the Fe-Tb composite material mainly plays a role in reducing the activation energy of combustion, catalyzing combustion, improving the combustion efficiency of coal and improving the sensible heat and heat productivity formed by combustion; the energy conservation and emission reduction of coal-fired enterprises are facilitated.
Drawings
FIG. 1 is a scanning electron microscope image of a Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive.
Detailed Description
The present invention will be described in further detail below.
Example one
The preparation method of the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive comprises the following steps of firstly, preparing FeCl with the concentration of 2 mol/L2Ethanol solution 1L, then 1mol tetra-n-butyl Titanate (TNB) was added, followed slowly by the addition of 0.1 mol/L concentration of TbCl3100ml of ethanol solution is evenly mixed, NaOH ethanol solution 1L with the concentration of 10 mol/L is dripped at the speed of 30ml/min, after aging is carried out for 24 hours, 0.67mol of hydrogen peroxide is dripped under the protection of nitrogen atmosphere, heat preservation is carried out for 1 hour at the temperature of 60-70 ℃, precipitates are separated by adopting a magnet, and after vacuum drying at the temperature of 75 ℃ and vacuum calcination at the temperature of 500 ℃, the prepared powder material is the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing and coke-removing additive.
The prepared Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive is added to a coal water slurry experimental furnace for testing, and the energy-saving and emission-reducing effects are shown in the following table.
Figure GDA0002491215390000031
Experimental data show that the additive also improves the caking property of the coke slag to a certain extent, and can effectively prevent the boiler from coking.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (7)

  1. A preparation method of a Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive is characterized by comprising the following steps: the method comprises the following steps:
    (1) preparation of FeCl2Adding tetrabutyl titanate and terbium salt ethanol solution into the ethanol solution, and uniformly mixing;
    (2) adding alkali liquor, and aging for more than 24 h;
    (3) dropping stoichiometric hydrogen peroxide under the protection of nitrogen atmosphere, and keeping the temperature at 60-70 ℃ for more than 1 h;
    (4) separating out precipitate by using a magnet;
    (5) after vacuum drying and vacuum calcining, the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive is prepared; vacuum calcining at 500 deg.C;
    in the terbium salt ethanol solution in the step (1), the terbium salt is TbCl3、TbF3、TbF4One or two of them.
  2. 2. The preparation method of the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive according to claim 1, characterized in that: in the step (2), the alkali solution added into the mixed solution is KOH ethanol solution or NaOH ethanol solution.
  3. 3. The Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive according to claim 1The preparation method is characterized by comprising the following steps: in step (1), FeCl2The concentration of the ethanol solution is 1-2 mol/L, the concentration of the terbium salt ethanol solution is 0.1-0.2 mol/L, and the concentration of the alkali liquor in the step (2) is 10 mol/L.
  4. 4. The preparation method of the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive according to claim 1, characterized in that: in the step (5), the vacuum drying condition is vacuum drying at 75-80 ℃.
  5. The Fe-Ti-Tb ternary composite coal-saving sulfur-fixing decoking additive is characterized in that: the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive is prepared by adopting the preparation method of the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive.
  6. 6. The Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive as claimed in claim 5, wherein: is a powdery material.
  7. 7. The application of the Fe-Ti-Tb ternary composite type coal-saving sulfur-fixing decoking additive according to claim 5 or 6, characterized in that: it can be used as coal-saving, sulfur-fixing and decoking additive for coal.
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US5079207A (en) * 1990-12-03 1992-01-07 The Standard Oil Company Catalyst for ammoxidation of paraffins
US5094989A (en) * 1990-12-21 1992-03-10 The Standard Oil Company Process for activation of catalysts
CN1346871A (en) * 2001-11-01 2002-05-01 谷振华 Energy-saving agent for reducing sulfur and coke in coal combustion
CN103160356B (en) * 2011-12-19 2016-05-25 湖南晟通科技集团有限公司 Integrated additive for fire coal of combustion-supporting solid sulfide denitration decoking and its preparation method and application
CN104371789A (en) * 2013-08-13 2015-02-25 杨林贵 Coke preventing and eliminating agent for saving energy
CN104910997B (en) * 2015-06-01 2017-03-29 江苏燃顺环保科技有限公司 A kind of coal-burning boiler decoking additive and preparation method thereof

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