CN108793789A - A kind of desulfurizing agent and preparation method thereof in cement production process - Google Patents
A kind of desulfurizing agent and preparation method thereof in cement production process Download PDFInfo
- Publication number
- CN108793789A CN108793789A CN201810657487.9A CN201810657487A CN108793789A CN 108793789 A CN108793789 A CN 108793789A CN 201810657487 A CN201810657487 A CN 201810657487A CN 108793789 A CN108793789 A CN 108793789A
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- Prior art keywords
- nitrate
- desulfurizing agent
- production process
- catalyst
- cement production
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Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/428—Organic materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
- C04B7/38—Preparing or treating the raw materials individually or as batches, e.g. mixing with fuel
- C04B7/42—Active ingredients added before, or during, the burning process
- C04B7/421—Inorganic materials
- C04B7/425—Acids or salts thereof
Abstract
The invention discloses a kind of desulfurizing agent in cement production process, raw material group becomes：Diethanol amine 10~18%, dispersant 0.5~1%, catalyst 0.2~0.5%, activating agent 20~35%, ferric nitrate 3~8%, cerous nitrate 5~8%, sodium carbonate 6~11%, magnesium nitrate 3~7%, surplus are water, total amount 100%；The percentage is mass percent.Use that catalyst its chemical stability added according to demand is good, halide ion without containing etching apparatus reduces alkaline components and SO under middle low-temperature condition2Reaction temperature, promote S02It is fully absorbed by raw material in preheater, reach solid sulphur and reduces SO2The purpose of discharge.
Description
Technical field
The present invention relates to a kind of desulfurizing agents and preparation method thereof in cement production process.
Background technology
Sulphur in quality coal in cement kiln systems is by the sulphur in raw material and fuel carrying raw material with organic sulfur compound, sulfide（Simple sulphur
Compound or complicated sulfide such as troilite）Or the form of sulfate exists, elemental sulfur can be ignored.
Sulfate present in raw material is generally do not form SO in pre-heating system2Gas generally can all enter kiln
System.Wherein a part of sulfate height temperate zone can decompose in kiln, the SO of generation2Gas is moved with kiln gas to kiln tail,
When reaching the temperature lower regions such as minimum two-stage preheater, be condensate on the lower raw material of temperature, and with the heavy collection of raw material into
Enter in kiln, forms a cycle between preheater and kiln, and undecomposed sulfate then can leave kiln system with clinker.
Existing sulphur otherwise in raw material（Mainly exist with sulphided form）, then SO can be generated by oxidation at 300 ~ 600 DEG C2
Gas occurs mainly in five（Four）The grade second level cyclone cylinder of preheater or the third level cyclone cylinder of six grades of preheaters.Raw material
In bring into sulphur oxidation generate SO2, can be partially absorbed when by higher level's cyclone cylinder, remaining is then with exhaust gas together from pre-
Hot device discharge.If exhaust gas is used for drying material, SO2It is further absorbed in raw material mill.It is less than 600 DEG C in temperature
In the case of, CaCO3To SO2Absorption efficiency to be far below CaO.And CaCO in two-stage preheater above3Resolution ratio pole
Low, only a small amount of CaO is got on by flue gas from high-temperature part band, therefore absorption efficiency is very low.Along with humidity at this time it is relatively low with
And the residence time before discharge is shorter, SO2Concentration of emission may be very high.If there is organic sulfur compound, oxidation behavior and sulphur
Iron ore is close.
American-European countries is to cement SO2Discharge pay close attention to earlier than China, according to Chinese GB4915-2004 cement production enterprises pair
SO2Concentration of emission requires to be less than 200 mg/m3, unit product discharge is no more than 0.6 kg/t.The numerous cement production enterprises in China
SO2 Emission reduction tasks it is very arduous.Therefore, it is necessary to develop a kind of cement that efficient, inexpensive, real stabilization can be permanently effective
Kiln desulfurizing agent, excitation raw material are desulphurizing activated, improve desulfuration efficiency.
Invention content
Purpose：To solve the deficiencies in the prior art, the present invention provides a kind of desulfurizing agent in cement production process.
Technical solution：In order to solve the above technical problems, the technical solution adopted by the present invention is：
A kind of desulfurizing agent in cement production process, it is characterised in that：The desulfurizing agent by diethanol amine, dispersant, urge
Agent, activating agent, ferric nitrate, cerous nitrate, sodium carbonate, magnesium nitrate and water reaction compounding mixing composition, raw material group become：Diethyl
Hydramine 10~18%, dispersant 0.5~1%, catalyst 0.2~0.5%, activating agent 20~35%, ferric nitrate 3~8%, cerous nitrate 5~
8%, sodium carbonate 6~11%, magnesium nitrate 3~7%, surplus is water, total amount 100%；The percentage is mass percent.
Preferably, the desulfurizing agent being used in cement production process, it is characterised in that：The catalyst is
One or several kinds of mixing in rhodium acetate, palladium, platinum chloride.
Preferably, the desulfurizing agent being used in cement production process, it is characterised in that：The activating agent is
One or two kinds of mixing in lithium nitrate, lanthanum nitrate.
Preferably, the desulfurizing agent being used in cement production process, it is characterised in that：The dispersant is
One or more of polycarboxylate, sodium soap and triethanolamine mix.
Preferably, the desulfurizing agent being used in cement production process, raw material group become：11% diethanol
Amine, 5% ferric nitrate, 7% cerous nitrate, 8% sodium carbonate, 28% activating agent, 0.2% catalyst, 1% dispersant, 4% magnesium nitrate, surplus are
Water, total amount 100%；The percentage is mass percent.
Preferably, the desulfurizing agent being used in cement production process, raw material group become：16% diethanol
Amine, 8% ferric nitrate, 5% cerous nitrate, 6% sodium carbonate, 24% activating agent, 0.4% catalyst, 1% dispersant, 7% magnesium nitrate, surplus are
Water, total amount 100%；The percentage is mass percent.
Preferably, the desulfurizing agent being used in cement production process, raw material group become：13% diethanol
Amine, 8% ferric nitrate, 5% cerous nitrate, 9% sodium carbonate, 33% activating agent, 0.3% catalyst, 0.7% dispersant, 6% magnesium nitrate, surplus are
Water, total amount 100%；The percentage is mass percent.
Preferably, the desulfurizing agent being used in cement production process, raw material group become：18% diethanol
Amine, 7% ferric nitrate, 5% cerous nitrate, 10% sodium carbonate, 23% activating agent, 0.5% catalyst, 0.8% dispersant, 7% magnesium nitrate, surplus
For water, total amount 100%；The percentage is mass percent.
The present invention also provides the preparation method for the desulfurizing agent in cement production process, step is：According to
Diethanol amine, dispersant, catalyst, activating agent, ferric nitrate, cerous nitrate, sodium carbonate, magnesium nitrate are dissolved in water by formula rate
In, be uniformly mixed to get.
The present invention provides a kind of desulfurizing agents and preparation method thereof in cement production process, from cement kiln desulfurization work
Skill is set out, and the production technology of cement production enterprise inherently carries desulfurization effect, and raw mill and preheater can own absorption raw materials
With the SO of fuel draining2Or when grinding machine shutdown, the higher requirement for being unable to reach national standard of discharge magnitude of sulphur takes one
Measure dry desulfurization, semi-dry desulphurization and the wet desulphurization of serial desulfurization.Dry desulfurizing process includes reactant insufflation, heat life
Expect insufflation etc.；Semi-dry desulphurization is mainly spray dry desulfurization method；Wet desulphurization includes the ammonia process of desulfurization, double alkali method desulfurizing, stone
The sulfur removal technologies such as grey lime-gypsum method.It analyzes and filters out and can excite in conjunction with these techniques and from the presently used desulfurizing agent of desulfurization
Desulfurizer activity, excellent catalytic effect and evaporable, cheap, nontoxic substance is not allowed.Addition diethanol amine can absorb first
SO2But also the lateral reactivity of raw material can be excited.It can disperse to penetrate into each contact of raw material secondly by dispersant is added
Face makes absorption SO2More fully.Catalyst is added again can improve absorption efficiency, and addition content is low, economical and practical.
Advantageous effect：Provided by the present invention for the desulfurizing agent in cement production process, chemical stability is good, addition content
It is low, it is nontoxic and pollution-free, SO can be promoted under middle low-temperature condition2It is fully absorbed by raw material in preheater, reaches solid sulphur and drop
Low SO2The purpose of discharge.It has the following advantages：
1）Actual amount is less than common desulfurizing agent.
2）Chemical stability is preferable, and catalyst is added and improves desulfurizer activity.
3）Price is low, non-corrosive, "dead", nontoxic, is not belonging to hazardous chemical.
Specific implementation mode
The present invention is illustrated with reference to example：Percentage is mass percent in the present invention.
Embodiment 1：A kind of desulfurizing agent in cement production process, raw material group become：11% diethanol amine, 5% nitre
Sour iron, 7% cerous nitrate, 8% sodium carbonate, 28% activating agent, 0.2% catalyst, 1% dispersant, 4% magnesium nitrate, surplus are water, always
Amount 100%；The percentage is mass percent, according to formula rate, by activating agent, catalyst, ferric nitrate, cerous nitrate, nitre
Sour iron, magnesium nitrate, sodium carbonate, dispersant are dissolved in water, and are uniformly mixed to get cement desulfurizing agent product 1.The product that will be obtained
1 cement producing line in certain cement plant enters is arranged liquid tank by kiln elevator, is delivered to product by metering pump and is promoted into kiln
Machine entrance, desulfurizing agent additive amount are the 0.1%-0.5% of cement slurry blending amount, and the discharge capacity depending on specific sulphur adds to calculate desulfurizing agent
Dosage.The discharge capacity being added before desulfurizing agent is SO2≥500mg/Nm³.After desulfurizing agent, discharge capacity can be reduced to SO2≤
100mg/Nm³。
Embodiment 2
A kind of desulfurizing agent and preparation method thereof in cement production process, raw material group becomes：16% diethanol amine, 8% nitre
Sour iron, 5% cerous nitrate, 6% sodium carbonate, 24% activating agent, 0.4% catalyst, 1% dispersant, 7% magnesium nitrate, surplus are water, always
Amount 100%；The percentage is mass percent.According to formula rate, by diethanol amine, dispersant, catalyst, activating agent,
Ferric nitrate, cerous nitrate, sodium carbonate, magnesium nitrate are dissolved in water, and are uniformly mixed to get cement desulfurizing agent product 2.
Embodiment 3
A kind of desulfurizing agent and preparation method thereof in cement production process, raw material group becomes：13% diethanol amine, 8% nitre
Sour iron, 5% cerous nitrate, 9% sodium carbonate, 33% activating agent, 0.3% catalyst, 0.7% dispersant, 6% magnesium nitrate, surplus are water,
Total amount 100%；The percentage is mass percent.According to formula rate, by diethanol amine, dispersant, catalyst, activity
Agent, ferric nitrate, cerous nitrate, sodium carbonate, magnesium nitrate are dissolved in water, and are uniformly mixed to get cement desulfurizing agent product 3.
Embodiment 4
A kind of desulfurizing agent and preparation method thereof in cement production process, raw material group becomes：18% diethanol amine, 7% nitre
Sour iron, 5% cerous nitrate, 10% sodium carbonate, 23% activating agent, 0.5% catalyst, 0.8% dispersant, 7% magnesium nitrate, surplus are
Water, total amount 100%；The percentage is mass percent.According to formula rate, by diethanol amine, dispersant, catalyst, work
Property agent, ferric nitrate, cerous nitrate, sodium carbonate, magnesium nitrate be dissolved in water, be uniformly mixed to get cement desulfurizing agent product 4.
Embodiment 5
A kind of desulfurizing agent and preparation method thereof in cement production process, raw material group becomes：10% diethanol amine, 3% nitre
Sour iron, 8% cerous nitrate, 11% sodium carbonate, 20% activating agent, 0.5% catalyst, 0.5% dispersant, 3% magnesium nitrate, surplus are
Water, total amount 100%；The percentage is mass percent.According to formula rate, by diethanol amine, dispersant, catalyst, work
Property agent, ferric nitrate, cerous nitrate, sodium carbonate, magnesium nitrate be dissolved in water, be uniformly mixed to get cement desulfurizing agent product 5.
The application method of the present invention, the addition content of cement desulfurizing agent are the 0.1%-0.5% of cement slurry blending amount.
The specifically used method and using effect of desulfurizing agent：
1, obtained product is entered in the cement producing line in certain cement plant and liquid tank is set by kiln elevator, will produced by metering pump
Product are delivered into kiln elevator entrance, and desulfurizing agent additive amount is the 0.1%-0.5% of cement slurry blending amount, depending on the discharge of specific sulphur
It measures to calculate desulfurizing agent additive amount.The discharge capacity being added before desulfurizing agent is SO2≥500mg/Nm³.After desulfurizing agent, discharge capacity
SO can be reduced to2≤100mg/Nm³。
2, liquid is arranged by the lime stone belt of the dispensing of the cement producing line raw material in certain cement plant in obtained product
Product is delivered on the lime stone belt of the dispensing of raw material by tank by metering pump, and desulfurizing agent additive amount blends for cement slurry
The 0.1%-0.5% of amount calculates desulfurizing agent additive amount depending on the discharge capacity of specific sulphur.The discharge capacity being added before desulfurizing agent is SO2≥
400mg/Nm³.After desulfurizing agent, discharge capacity can be reduced to SO2≤100mg/Nm³。
The present invention is disclosed with preferred embodiment above, so it is not intended to limiting the invention, all to use equivalent replacement
Or the technical solution that equivalent transformation mode is obtained, it is within the scope of the present invention.
Claims (9)
1. a kind of desulfurizing agent in cement production process, it is characterised in that：The desulfurizing agent by diethanol amine, dispersant,
Catalyst, activating agent, ferric nitrate, cerous nitrate, sodium carbonate, magnesium nitrate and water reaction compounding mixing composition, raw material group become：Two
Ethanol amine 10~18%, dispersant 0.5~1%, catalyst 0.2~0.5%, activating agent 20~35%, ferric nitrate 3~8%, cerous nitrate 5
~8%, sodium carbonate 6~11%, magnesium nitrate 3~7%, surplus is water, total amount 100%；The percentage is mass percent.
2. the desulfurizing agent according to claim 1 in cement production process, it is characterised in that：The catalyst is vinegar
One or several kinds of mixing in sour rhodium, palladium, platinum chloride.
3. the desulfurizing agent according to claim 1 in cement production process, it is characterised in that：The activating agent is nitre
One or two kinds of mixing in sour lithium, lanthanum nitrate.
4. the desulfurizing agent according to claim 1 in cement production process, it is characterised in that：The dispersant is poly-
One or more of carboxylate, sodium soap and triethanolamine mix.
5. the desulfurizing agent according to claim 1 in cement production process, raw material group becomes：11% diethanol amine,
5% ferric nitrate, 7% cerous nitrate, 8% sodium carbonate, 28% activating agent, 0.2% catalyst, 1% dispersant, 4% magnesium nitrate, surplus are water, always
Amount 100%；The percentage is mass percent.
6. the desulfurizing agent according to claim 1 in cement production process, raw material group becomes：16% diethanol amine,
8% ferric nitrate, 5% cerous nitrate, 6% sodium carbonate, 24% activating agent, 0.4% catalyst, 1% dispersant, 7% magnesium nitrate, surplus are water, always
Amount 100%；The percentage is mass percent.
7. the desulfurizing agent according to claim 1 in cement production process, raw material group becomes：13% diethanol amine,
8% ferric nitrate, 5% cerous nitrate, 9% sodium carbonate, 33% activating agent, 0.3% catalyst, 0.7% dispersant, 6% magnesium nitrate, surplus are water,
Total amount 100%；The percentage is mass percent.
8. the desulfurizing agent according to claim 1 in cement production process, raw material group becomes：18% diethanol amine,
7% ferric nitrate, 5% cerous nitrate, 10% sodium carbonate, 23% activating agent, 0.5% catalyst, 0.8% dispersant, 7% magnesium nitrate, surplus are
Water, total amount 100%；The percentage is mass percent.
9. the preparation method according to claim 1-8 any one of them for the desulfurizing agent in cement production process, step
For：It is according to formula rate, diethanol amine, dispersant, catalyst, activating agent, ferric nitrate, cerous nitrate, sodium carbonate, magnesium nitrate is molten
Solution in water, be uniformly mixed to get.
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| CN201810657487.9A CN108793789A (en) | 2018-06-25 | 2018-06-25 | A kind of desulfurizing agent and preparation method thereof in cement production process |
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Cited By (5)
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| CN110327764A (en) * | 2019-07-17 | 2019-10-15 | 南京永能新材料有限公司 | A kind of composite water stall fume desulfurizing agent and preparation method thereof |
| CN112058043A (en) * | 2020-08-25 | 2020-12-11 | 北京金隅水泥节能科技有限公司 | Desulfurizing agent and preparation method thereof |
| CN113416010A (en) * | 2021-07-31 | 2021-09-21 | 山西天润恒德新材料有限公司 | Raw material grinding aid for cement clinker firing process |
| CN115445420A (en) * | 2022-07-07 | 2022-12-09 | 南京永能新材料有限公司 | Cement kiln flue gas liquid desulfurizer and preparation method thereof |
| CN116040968A (en) * | 2023-02-01 | 2023-05-02 | 山东中岩建材科技有限公司 | Cement raw material liquid grinding aid and preparation method and application thereof |
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| CN116040968B (en) * | 2023-02-01 | 2024-03-29 | 山东中岩建材科技有限公司 | Cement raw material liquid grinding aid and preparation method and application thereof |
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