CN105838476A - High-temperature sulphur-fixing agent - Google Patents
High-temperature sulphur-fixing agent Download PDFInfo
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- CN105838476A CN105838476A CN201610462564.6A CN201610462564A CN105838476A CN 105838476 A CN105838476 A CN 105838476A CN 201610462564 A CN201610462564 A CN 201610462564A CN 105838476 A CN105838476 A CN 105838476A
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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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- 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
- C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
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Abstract
The invention discloses a high-temperature sulphur-fixing agent which is prepared from the following components in parts by weight: 4-7 parts of kaolin, 3-6 parts of kieselguhr, 2-4 parts of anorthite, 2-5 parts of talcum powder, 7-9 parts of calcium oxide, 1-3 parts of zinc oxide, 4-8 parts of strontium carbonate, 3-8 parts of barium hydroxide, 0.3-0.5 part of potassium sulphate, 0.2-0.5 part of vanadium pentoxide, 4-9 parts of niobium pentoxide, 0.3-0.6 part of aluminite powder, 0.2-0.5 part of iron powder microballoon sphere, 0.1-0.3 part of calcium titanate, 20-25 parts of ethyl alcohol, 2-4 parts of sodium dodecyl benzene sulfonate, 1-3 parts of nanometer titania and 2-4 parts of nano calcium carbonate. The sulphur-fixing agent disclosed by the invention has a reasonable prescription, is high temperature resistant, good in high-temperature desulfurization effect, and favorable in development prospect of coal sulphur fixing.
Description
Technical field
The present invention relates to a kind of high-temperature desulfurization agent, belong to control atmospheric pollution technical field.
Background technology
Coal is one of main energy sources of China, is also to apply the most common energy former in modern industry
Material, but its main Land use systems is burning, and burn and can produce flue dust, sulfur dioxide (SO2)、
NOxEtc. atmosphere pollution.The acid rain etc. that these atmosphere pollutions are easily formed, causes atmospheric environment
Great harm, has had a strong impact on the quality of environment for human survival, has destroyed ecological balance.For solving
Certainly this technical barrier, China uses coal combustion and sulfur fixation technology to control sulfur dioxide (SO2) discharge,
Reduce atmospheric pollution.
At present, the sulfur solidifying technique of domestic coal-burning power plant has: desulfurization before combustion, sulphur fixation in coal combustion and flue gas desulfurization.
Wherein, desulfurization before combustion can remove the inorganic sulfur of 40%～60%；Though desulfurization desulfurized effect is good after combustion, de-
Sulfur rate is up to more than 80%, but owing to investment is big, operating cost is high, and waste gypsum after desulfurization
Problem of outlet, limits the application of its enterprise at home to a certain extent；Desulfurization in combustion, in fire coal
Increase sulphur-fixing agent and can control sulfur dioxide (SO2) discharge, convenient and easy, small investment and operation
Expense is low.Wherein, calcium based sulphur-fixation reagent is the most frequently used sulphur-fixing agent, and this is owing to calcium based sulphur-fixation reagent is cheap
It is easy to get.Common calcium based sulphur-fixation reagent has limestone, dolomite, quick lime etc., and it is mainly by oxygen
Change calcium (CaO) sulfur dioxide absorption (SO2), generate calcium sulfate (CaSO4), it is achieved control two
Sulfur oxide (SO2) purpose discharged.But under conditions of high temperature, sulfur retention products calcium sulfate (CaSO4)
Easily twice decomposition, reduces sulfur-fixing rate.
In order to solve this technical barrier, people carry out in-depth study to sulphur-fixing agent.In recent years, people
On sulphur-fixing agent, obtain certain Research Achievement, as Chinese patent CN 1252229C disclose " combustion
Coal compound sulphur-fixing agent and preparation method thereof ", this sulphur-fixing agent is by being ground into compound less than 1mm of granularity
Carbonate, calcium carbonate, calcium oxide and magnesium carbonate uniformly mix composition, can be respectively in different ignition temperatures
The sulfur dioxide that section produces in fully absorbing coal furnace, thus reach to reduce in coal fire discharged flue gas
Content of sulfur dioxide, reduces the purpose of environmental pollution.Although this sulphur-fixing agent component raw material is easy to get, preparation
Simple process, low production cost, but its sulfur-fixing rate less than ideal under the high temperature conditions, this
Hinder popularization and the application of sulphur-fixing agent to a certain extent.Therefore, continue to explore and research sulphur-fixing agent
It is the most valuable.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the technical problem to be solved is to propose one
It is resistant to high-temperature, and the high-temperature desulfurization agent that sulfur-fixing rate is high.
A kind of high-temperature desulfurization agent, is made up of each component of following weight: Kaolin 4～7 parts,
Kieselguhr 3～6 parts, anorthite 2～4 parts, Pulvis Talci 2～5 parts, calcium oxide 7～9 parts, oxidation
Zinc 1～3 parts, strontium carbonate 4～8 parts, barium hydroxide 3～8 parts, potassium sulfate 0.3～0.5 part, five
V 2 O 0.2～0.5 part, niobium pentaoxide 4～9 parts, aluminium powder 0.3～0.6 part, iron powder microsphere
0.2～0.5 part, calcium titanate 0.1～0.3 part, ethanol 20～25 parts, dodecylbenzene sodium sulfonate 2～
4 parts, nano titanium oxide 1～3 parts, nano-calcium carbonate 2～4 parts.
Further,
A kind of high-temperature desulfurization agent, is made up of each component of following weight: Kaolin 4～6 parts,
Kieselguhr 3～5 parts, anorthite 2～4 parts, Pulvis Talci 2～4 parts, calcium oxide 7～9 parts, oxidation
Zinc 1～3 parts, strontium carbonate 4～6 parts, barium hydroxide 3～7 parts, potassium sulfate 0.3～0.5 part, five
V 2 O 0.2～0.4 part, niobium pentaoxide 4～8 parts, aluminium powder 0.3～0.5 part, iron powder microsphere
0.2～0.4 part, calcium titanate 0.1～0.3 part, ethanol 20～23 parts, dodecylbenzene sodium sulfonate 2～
4 parts, nano titanium oxide 1～3 parts, nano-calcium carbonate 2～4 parts.
Further,
A kind of high-temperature desulfurization agent, is made up of each component of following weight: Kaolin 5 parts, silicon
Diatomaceous earth 4 parts, anorthite 3 parts, Pulvis Talci 3 parts, calcium oxide 8 parts, zinc oxide 2 parts, strontium carbonate
6 parts, barium hydroxide 5 parts, potassium sulfate 0.4 part, vanadic anhydride 0.3 part, niobium pentaoxide 6
Part, aluminium powder 0.4 part, iron powder microsphere 0.3 part, calcium titanate 0.2 part, ethanol 22 parts, dodecyl
Benzene sulfonic acid sodium salt 3 parts, nano titanium oxide 2 parts, nano-calcium carbonate 3 parts.
Wherein, described iron powder microsphere by iron powder 3～5 parts, magnesium oxide 1～3 parts, aluminium oxide 1～
3 parts of nodularizations form；Described Kaolin, kieselguhr, anorthite, Pulvis Talci, calcium oxide, oxidation
Zinc, strontium carbonate, barium hydroxide, potassium sulfate, vanadic anhydride, niobium pentaoxide, aluminium powder, metatitanic acid
Calcium, the mesh number of dodecylbenzene sodium sulfonate are 100～200 mesh；Described nano titanium oxide, receive
The particle diameter of rice calcium carbonate is 50～100nm.
The high-temperature desulfurization agent principle of the present invention is as follows: after firming agent and coal are sufficiently mixed, and adds burner hearth
In burn, in combustion process:
1, when temperature is less than 300 DEG C, ethanol can promote coal combustion, and dodecylbenzene sodium sulfonate is not
It is only capable of reduction surface tension, promotes length of penetration, the most combustion-supporting effect, improve calory burning,
Meanwhile, iron powder microsphere, kieselguhr have good adsorptivity, can adsorb release in combustion process big
Gas pollutant；
2, when temperature 300～500 DEG C, the SO that calcium oxide is decomposed to form with fat sulfur in coal2Reaction,
Generate CaSO4；
3, when temperature 500～950 DEG C, first, Pulvis Talci forms molten silicate body, and is coated with
On surface, thus realize solid sulfur purpose.Secondly, zinc oxide is sulfur fixation in reducing atmosphere, and with
The solid sulfur of the form of ZnS, meanwhile, zinc oxide also acts as catalytic action.Then, barium hydroxide energy and sulfur
Oxide forms BaSO4, BaSO4Coal-fired structure can be made to occur with other sulfate formation eutectics
Changing, hole increases, and increases the contact area of oxysulfide and sulphur-fixing agent, thus improves sulfur-fixing rate.
Finally, vanadic anhydride, potassium sulfate and kieselguhr generation coordinative role, make sulfur dioxide become three oxygen
Change sulfur, so that it forms stable compound with firming agent, and then improve sulfur-fixing rate；
4, when temperature is more than 1100 DEG C, first, Kaolin, anorthite can be with calcium oxide, iron powders
The composition generation solid state reactions such as microsphere, form 3CaO.3Al2O3.CaSO4、2CaO.Al2O3.SiO2、
CaFe3(SiO4) high-temperature-phase such as OH, thus improve sulfur-fixing rate at high temperature；Meanwhile, Kaolin, anorthite
Middle Na+、K+、Mg2+Plasma, it is possible to cause more crystal defect, beneficially Ca2+Diffusion,
Improve sulfur-fixing rate.Secondly, strontium carbonate resolves into strontium oxide, with SOxReaction generates SrSO4, enter one
Step improves sulfur-fixing rate.Again, calcium titanate, niobium pentaoxide present different phases in different temperature,
Wherein, niobium pentaoxide is α phase at 800～900 DEG C, and 1000～1150 DEG C is β phase, 1200～
1250 DEG C is γ phase.Different phase transformations, changes texture of coal, increases crystal defect, improves sulfur-fixing rate；
Then, aluminium powder is in coal combustion process, by easily causing microexplosion under high temperature action, in the effect of microexplosion power
Under make coal ftracture, make coal surface be easier to sulphur-fixing agent and carry out chemical reaction, thus improve sulfur-fixing rate.
Finally, nano titanium oxide, nano-calcium carbonate make the specific surface area of coal become big, prevent product CaSO4
The duct on blocking CaO surface, improves sulfur-fixing rate.
Compared with prior art, the invention has the beneficial effects as follows:
1, general sulphur-fixing agent is to be oxidation of the sulfide into CaSO4, this product is easy secondary when high temperature
Decompose.Sulphur-fixing agent of the present invention is by sulfide 3CaO.3Al2O3.CaSO4、2CaO.Al2O3.SiO2、
CaFe3(SiO4) high-temperature-phase such as OH, under these product high temperature, thing is stable mutually, thus improves high-temperature fixed sulfur
Rate.
2, Na in Kaolin, anorthite+、K+、Mg2+Plasma, it is possible to cause more crystal
Defect, beneficially Ca2+Diffusion, improves sulfur-fixing rate.
3, calcium titanate, niobium pentaoxide present different phases, wherein, five oxidations in different temperature
Two niobiums are α phases at 800～900 DEG C, and 1000～1150 DEG C is β phase, and 1200～1250 DEG C is γ phase.
Different phase transformations, changes texture of coal, increases crystal defect, improves sulfur-fixing rate.
4, aluminium powder is in coal combustion process, by easily causing microexplosion under high temperature action, at the work of microexplosion power
Make coal ftracture under with, make coal surface be easier to sulphur-fixing agent and carry out chemical reaction, thus improve sulfur-fixing rate.
5, improve sulfur-fixing rate, reduce SO2Discharge, decrease atmospheric pollution, also reduce meanwhile
The consumption of the energy.This be due to the present invention sulphur-fixing agent in combustion, not only control SO2's
Discharge, and progressively carry out the solid state reaction of exothermic reaction, reduce heat dissipation, improve the efficiency of coal.
Detailed description of the invention
During use, the incorporation of sulphur-fixing agent is 3～6%.
Embodiment 1
In this enforcement, iron powder microsphere is formed by iron powder 4 parts, magnesium oxide 2 parts, 2 parts of nodularizations of aluminium oxide；
Kaolin, kieselguhr, anorthite, Pulvis Talci, calcium oxide, zinc oxide, strontium carbonate, barium hydroxide,
Potassium sulfate, vanadic anhydride, niobium pentaoxide, aluminium powder, calcium titanate, dodecylbenzene sodium sulfonate
Mesh number is 120 mesh；Nano titanium oxide, the particle diameter of nano-calcium carbonate are 80nm.
A kind of high-temperature desulfurization agent, is made up of each component of following weight: Kaolin 5 parts, silicon
Diatomaceous earth 4 parts, anorthite 3 parts, Pulvis Talci 3 parts, calcium oxide 8 parts, zinc oxide 2 parts, strontium carbonate
6 parts, barium hydroxide 5 parts, potassium sulfate 0.4 part, vanadic anhydride 0.3 part, niobium pentaoxide 6
Part, aluminium powder 0.4 part, iron powder microsphere 0.3 part, calcium titanate 0.2 part, ethanol 22 parts, dodecyl
Benzene sulfonic acid sodium salt 3 parts, nano titanium oxide 2 parts, nano-calcium carbonate 3 parts.
Embodiment 2
In this enforcement, iron powder microsphere is formed by iron powder 3 parts, magnesium oxide 1 part, 1 part of nodularization of aluminium oxide；
Kaolin, kieselguhr, anorthite, Pulvis Talci, calcium oxide, zinc oxide, strontium carbonate, barium hydroxide,
Potassium sulfate, vanadic anhydride, niobium pentaoxide, aluminium powder, calcium titanate, dodecylbenzene sodium sulfonate
Mesh number is 100 mesh；Nano titanium oxide, the particle diameter of nano-calcium carbonate are 50nm.
A kind of high-temperature desulfurization agent, is made up of each component of following weight: Kaolin 4 parts, silicon
Diatomaceous earth 3 parts, anorthite 2 parts, Pulvis Talci 2 parts, calcium oxide 7 parts, zinc oxide 1 part, strontium carbonate
4 parts, barium hydroxide 3 parts, potassium sulfate 0.3 part, vanadic anhydride 0.2 part, niobium pentaoxide 4
Part, aluminium powder 0.3 part, iron powder microsphere 0.2 part, calcium titanate 0.1 part, ethanol 20 parts, dodecyl
Benzene sulfonic acid sodium salt 2 parts, nano titanium oxide 1 part, nano-calcium carbonate 2 parts.
Embodiment 3
In this enforcement, iron powder microsphere is formed by iron powder 5 parts, magnesium oxide 3 parts, 3 parts of nodularizations of aluminium oxide；
Kaolin, kieselguhr, anorthite, Pulvis Talci, calcium oxide, zinc oxide, strontium carbonate, barium hydroxide,
Potassium sulfate, vanadic anhydride, niobium pentaoxide, aluminium powder, calcium titanate, dodecylbenzene sodium sulfonate
Mesh number is 200 mesh；Nano titanium oxide, the particle diameter of nano-calcium carbonate are 100nm.
A kind of high-temperature desulfurization agent, is made up of each component of following weight: Kaolin 7 parts, silicon
Diatomaceous earth 6 parts, anorthite 4 parts, Pulvis Talci 5 parts, calcium oxide 9 parts, zinc oxide 3 parts, strontium carbonate
8 parts, barium hydroxide 8 parts, potassium sulfate 0.5 part, vanadic anhydride 0.5 part, niobium pentaoxide 9
Part, aluminium powder 0.6 part, iron powder microsphere 0.5 part, calcium titanate 0.3 part, ethanol 25 parts, dodecyl
Benzene sulfonic acid sodium salt 4 parts, nano titanium oxide 3 parts, nano-calcium carbonate 4 parts.
Embodiment 4
In this enforcement, iron powder microsphere is formed by iron powder 5 parts, magnesium oxide 3 parts, 3 parts of nodularizations of aluminium oxide；
Kaolin, kieselguhr, anorthite, Pulvis Talci, calcium oxide, zinc oxide, strontium carbonate, barium hydroxide,
Potassium sulfate, vanadic anhydride, niobium pentaoxide, aluminium powder, calcium titanate, dodecylbenzene sodium sulfonate
Mesh number is 200 mesh；Nano titanium oxide, the particle diameter of nano-calcium carbonate are 100nm.
A kind of high-temperature desulfurization agent, is made up of each component of following weight: Kaolin 6 parts, silicon
Diatomaceous earth 5 parts, anorthite 4 parts, Pulvis Talci 4 parts, calcium oxide 9 parts, zinc oxide 3 parts, strontium carbonate
6 parts, barium hydroxide 7 parts, potassium sulfate 0.5 part, vanadic anhydride 0.4 part, niobium pentaoxide 8
Part, aluminium powder 0.5 part, iron powder microsphere 0.4 part, calcium titanate 0.3 part, ethanol 23 parts, dodecyl
Benzene sulfonic acid sodium salt 4 parts, nano titanium oxide 3 parts, nano-calcium carbonate 4 parts.
It addition, for the effect that sulphur-fixing agent of the present invention is described, applicant carried out test, result of the test
As shown in table 1:
Table 1 sulphur-fixing agent result of the test
| Sulphur-fixing agent type | Volume (%) | Temperature (DEG C) | Sulfur-fixing rate (%) |
| Embodiment 1 | 5 | 1200 | 82 |
| Embodiment 2 | 3 | 1150 | 81 |
| Embodiment 3 | 4 | 1100 | 80 |
| Embodiment 4 | 6 | 1180 | 81 |
| Background technology | 4 | 1100 | 73 |
As known from Table 1, compared with background of invention, the present invention at high temperature has high solid sulfur
Rate, this demonstrates sulphur-fixing agent provided by the present invention and has significant captured sulfur result.
Certainly, it is that the preferred embodiments of the disclosure is described in detail, not with this above
Limit the practical range of the present invention, the equivalence change that all principles under this invention, structure and structure are made
Change, all should be covered by protection scope of the present invention.
Claims (5)
1. a high-temperature desulfurization agent, it is characterised in that: it is made up of each component of following weight:
Kaolin 4～7 parts, kieselguhr 3～6 parts, anorthite 2～4 parts, Pulvis Talci 2～5 parts, oxidation
Calcium 7～9 parts, zinc oxide 1～3 parts, strontium carbonate 4～8 parts, barium hydroxide 3～8 parts, potassium sulfate
0.3～0.5 part, vanadic anhydride 0.2～0.5 part, niobium pentaoxide 4～9 parts, aluminium powder 0.3～0.6
Part, iron powder microsphere 0.2～0.5 part, calcium titanate 0.1～0.3 part, ethanol 20～25 parts, dodecane
Base benzene sulfonic acid sodium salt 2～4 parts, nano titanium oxide 1～3 parts, nano-calcium carbonate 2～4 parts.
High-temperature desulfurization agent the most according to claim 1, it is characterised in that: by following weight portion
Each component of proportioning is made: Kaolin 4～6 parts, kieselguhr 3～5 parts, anorthite 2～4 parts,
Pulvis Talci 2～4 parts, calcium oxide 7～9 parts, zinc oxide 1～3 parts, strontium carbonate 4～6 parts, hydrogen-oxygen
Change barium 3～7 parts, potassium sulfate 0.3～0.5 part, vanadic anhydride 0.2～0.4 part, niobium pentaoxide
4～8 parts, aluminium powder 0.3～0.5 part, iron powder microsphere 0.2～0.4 part, calcium titanate 0.1～0.3 part,
Ethanol 20～23 parts, dodecylbenzene sodium sulfonate 2～4 parts, nano titanium oxide 1～3 parts, receive
Rice calcium carbonate 2～4 parts.
High-temperature desulfurization agent the most according to claim 1, it is characterised in that: by following weight portion
Each component of proportioning is made: Kaolin 5 parts, 4 parts of kieselguhr, anorthite 3 parts, Pulvis Talci 3
Part, calcium oxide 8 parts, zinc oxide 2 parts, strontium carbonate 6 parts, barium hydroxide 5 parts, potassium sulfate 0.4
Part, vanadic anhydride 0.3 part, niobium pentaoxide 6 parts, aluminium powder 0.4 part, iron powder microsphere 0.3 part,
Calcium titanate 0.2 part, ethanol 22 parts, dodecylbenzene sodium sulfonate 3 parts, nano titanium oxide 2 parts,
Nano-calcium carbonate 3 parts.
High-temperature desulfurization agent the most according to claim 3, it is characterised in that: described iron powder is micro-
Ball is formed by iron powder 3～5 parts, magnesium oxide 1～3 parts, aluminium oxide 1～3 parts of nodularizations.
High-temperature desulfurization agent the most according to claim 3, it is characterised in that: described Kaolin,
Kieselguhr, anorthite, Pulvis Talci, calcium oxide, zinc oxide, strontium carbonate, barium hydroxide, potassium sulfate,
Vanadic anhydride, niobium pentaoxide, aluminium powder, calcium titanate, the mesh number of dodecylbenzene sodium sulfonate are
100～200 mesh.
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Citations (5)
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|---|---|---|---|---|
| JP2003064386A (en) * | 2001-08-23 | 2003-03-05 | Mitsubishi Heavy Ind Ltd | Desulfurizing agent for removing sulfur compound in fuel gas, and fuel cell power generation system utilizing the agent |
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| CN103013610A (en) * | 2012-11-30 | 2013-04-03 | 内蒙古科技大学 | Method for preparing biomass briquette by virtue of lower-calorific-value coal |
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2016
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| JP2003064386A (en) * | 2001-08-23 | 2003-03-05 | Mitsubishi Heavy Ind Ltd | Desulfurizing agent for removing sulfur compound in fuel gas, and fuel cell power generation system utilizing the agent |
| JP2004089778A (en) * | 2002-08-29 | 2004-03-25 | Rikogaku Shinkokai | Desulfurization/denitrification agent and desulfurization/denitrification method |
| CN102041131A (en) * | 2011-01-21 | 2011-05-04 | 洛阳万山高新技术应用工程有限公司 | High-temperature sulfur solidifying agent for desulfurization in coal blending burner |
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Application publication date: 20160810 |