CN111348848A - Method for using high-sulfur raw material for cement kiln - Google Patents
Method for using high-sulfur raw material for cement kiln Download PDFInfo
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- CN111348848A CN111348848A CN202010216877.XA CN202010216877A CN111348848A CN 111348848 A CN111348848 A CN 111348848A CN 202010216877 A CN202010216877 A CN 202010216877A CN 111348848 A CN111348848 A CN 111348848A
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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
- C04B7/32—Aluminous cements
- C04B7/323—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
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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
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/26—Cements from oil shales, residues or waste other than slag from raw materials containing flue dust, i.e. fly ash
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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
- C04B7/421—Inorganic materials
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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
- C04B7/421—Inorganic materials
- C04B7/424—Oxides, Hydroxides
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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
- C04B7/421—Inorganic materials
- C04B7/425—Acids or salts thereof
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Treating Waste Gases (AREA)
Abstract
A method for using high-sulfur raw materials for a cement kiln utilizes a raw material preparation system, a raw material warehouse, a raw material kiln entering system, a preheater system, a kiln tail smoke exhaust channel and dust collector equipment of the existing dry-process cement kiln, and specifically comprises the following steps: (1) preparing catalytic powder or catalytic aqueous solution from metal compounds; (2) spraying or scattering the raw materials or the raw meal or the flue gas powder particles on a raw meal preparation system or a raw meal warehouse or a raw meal kiln entering system or a C1, C2 and C3 preheater system or a kiln tail flue gas exhaust channel; (3) catalytic powder or catalytic aqueous solution sprayed or sprinkled in raw materials or raw materials for catalyzing SO at high temperature2Molecule, O2Molecule, CaCO3The powder and CaO powder are subjected to chemical reaction to generate stable CaSO4Microparticles; (4) generated CaSO4The particles are collected by a dust collector and then enter the cement clinker system again. The invention has the characteristics of low cost, reliable operation and the like, and can solve the problem of the cement kiln tail flue gas SO2And (4) the problem of excessive emission.
Description
Technical Field
The invention relates to the field of air pollution control, in particular to a method for using a high-sulfur raw material for a cement kiln.
Background
Limestone is the main raw material of cement plants, accounting for about 80% of all raw materials, and limestone used in most cement plants has low sulfur content and cannot cause SO2The content of sulfur in the high-sulfur limestone exceeds the standard, but the high-quality limestone is a non-renewable mineral resource, is not only used for cement production, but also used in the industries of thermal power, metallurgy, papermaking, steel, pharmacy, food additives, sugar manufacturing, chemical industry, pesticide and the like, and some cement plants have to use low-grade high-sulfur limestone with the sulfur content of 0.2-3.0 percent along with the exhaustion of the high-quality limestone around the cement plants, SO that SO in the smoke of the cement kiln is caused2The discharge concentration is as high as 1000-4000mg/Nm3China 'atmospheric pollutant emission Standard for Cement industry' (GB 4915-2013) stipulates SO in kiln tail flue gas of cement kilns2The discharge concentration is less than or equal to 200mg/Nm3The unit clinker discharge amount needs to be lower than 0.6kg/t, and SO in the kiln tail flue gas of the special area cement kiln2The discharge concentration is less than or equal to 100mg/Nm3. Therefore, the development of a method which has low cost and reliable operation and can solve the problem of the tail flue gas SO of the cement kiln is urgently needed2The method for using high-sulfur raw materials in the cement kiln with the problem of excessive discharge.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cement kiln tail flue gas SO with low cost and reliable operation2The method for using high-sulfur raw materials in the cement kiln with the problem of excessive discharge.
The existing dry method cement kiln production system is a desulfurization system, the used limestone raw material accounts for 70% of all ingredients, and all the raw materials are conveyed to a raw material mill by a conveying belt after being blended from a raw material warehouse and are ground into raw material fine powder of 80 microns; the ground fine powder enters a kiln tail dust collector for collection under the conditions of drying and conveying kiln tail flue gas; conveying the collected raw material fine powder to a raw material warehouse by a conveying belt or a lifter; the raw material in the raw material storehouse is homogenized by a homogenizing device and then is conveyed to a pre-heater of an outlet C2 by a conveying belt, a lifter and a feeding chuteAnd an air outlet, and the cement clinker is preheated by preheaters C1, C2, C3, C4 and C5 and enters the rotary kiln through a decomposing furnace to generate the cement clinker. Wherein the sulfide in the high-sulfur ore is mainly decomposed and oxidized at C2 and C3 to form SO2SO formed2And the flue gas together with the kiln tail is finally discharged into the atmosphere through a C2, a C1, a humidifying tower (and a waste heat boiler), a high-temperature fan, (a raw material mill), a kiln tail dust collector, a kiln tail fan and a chimney. Wherein when the sulfur content of the raw material is not high, SO is added2CaCO in flue gas3And CaO powder particles (generally, the C1 preheater discharges CaCO along with the kiln tail flue gas3When the CaO powder accounts for 2-5% of the fed amount and is fully absorbed, SO is generated2The discharge concentration is less than or equal to 200mg/Nm3Meets the emission standard, and when high-sulfur ore is used, SO is decomposed due to high sulfide content2Can not be absorbed by CaCO in flue gas3And when CaO powder particles are fully absorbed, the emission exceeds the standard.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for using high-sulfur raw materials for a cement kiln utilizes equipment such as a raw material preparation system, a raw material warehouse, a raw material kiln entering system, a preheater system, a kiln tail smoke exhaust channel, a dust collector and the like of the existing dry-process cement kiln, and specifically comprises the following steps:
(1) preparing catalytic powder or catalytic aqueous solution by using a metal compound, wherein the metal compound is a compound of manganese, iron, copper or zinc;
(2) spraying or scattering the catalytic powder or catalytic water agent obtained in the step (1) on raw material preparation system or raw material warehouse or raw material kiln system or raw material of a preheater system of C1, C2 and C3 or raw material of a smoke exhaust channel at the tail of a kiln or raw material or smoke powder particles;
(3) the catalytic powder or catalytic water agent sprayed or scattered in the raw materials or the raw materials is finally mixed with the kiln tail flue gas at the preheaters of C1, C2 and C3 to realize the mixing of the catalytic powder or catalytic water agent and CaCO in the kiln tail flue gas3Mixing with CaO powder, and catalyzing SO at high temperature (generally over 100 deg.C)2Molecule, O2Molecule, CaCO3The powder and CaO powder are subjected to chemical reaction to generate stable CaSO4Microparticles;
(4) generated CaSO4The particles are collected by a dust collector and then enter the cement kiln again to finally become cement clinker.
Further, in the step (1), the metal compound may be an oxide or a metal salt, wherein a soluble metal salt is preferred, so as to improve the mixing effect in the step (2).
Further, in the step (1), the metal compound may be a metal compound ore, and is prepared together with the raw meal in a raw material warehouse and a raw meal preparation system, and is pulverized into metal compound powder in a raw meal mill for use as the catalytic powder.
Further, in the step (1), ammonia or amine and the like can be added into the catalytic water agent; or in the step (2), ammonia substances or amine substances and the like are independently sprayed to form the absorbent, so that the desulfurization effect is improved.
Further, in the step (1), a surfactant and/or an aggregating agent may be added to the aqueous catalytic agent; or in the step (2), the surfactant and/or the agglomerating agent are independently sprayed, so that the dust collecting effect of the dust collector is improved.
Further, in the step (2), the raw material preparation system refers to a whole process of preparing raw materials from limestone raw materials, and comprises a raw material warehouse, a conveying belt, a raw material mill and a raw material warehouse system; the raw material kiln feeding system is equipment in the whole process from raw material discharged from a raw material warehouse to raw material feeding into a preheater system, and comprises a material conveying belt, a material conveying hoister and a chute; the kiln tail smoke exhaust channel refers to a pipeline and equipment through which kiln tail smoke flows from the preheater to the kiln tail dust collector.
Further, in the step (2), the dosage of the catalytic powder or catalytic water agent is prepared according to the sulfur content of the high-sulfur ore, the sulfur content of the kiln tail flue gas raw material and the kiln entering amount of the raw material, and preferably the preparation proportion of the catalyst is 0.01-10 mol/ton of raw material; the specific concentration is determined by the initial SO of the kiln tail flue gas2The concentration is adjusted.
Furthermore, in the step (2), the spraying or scattering points can be arranged at one or more than two points and are arranged on equipment such as a raw material preparation system, a raw material warehouse, a raw material kiln entering system, a preheater system, a kiln tail smoke exhaust channel and the like.
The technical principle is as follows:
although the kiln tail flue gas discharged from the C1 preheater contains a large amount of CaCO3Powder, CaO powder (e.g. about 4-8 tons in 2500 type cement kiln), but due to SO2Molecules are not easily converted to SO at high temperatures without catalyst3Molecule, or SO2Molecule and CaCO3CaSO produced by powder reaction3The molecules are unstable and are decomposed again, and finally, the kiln tail flue gas contains a large amount of CaCO3The powder and CaO powder can not play the role of a desulfurizer, and particularly SO is caused when high-sulfur ores are adopted2The emission exceeds the standard. The invention utilizes the catalytic characteristics of manganese, iron, copper and zinc, and by spreading catalyst powder or spraying a catalytic water agent on raw materials and raw materials, the catalysts and the raw materials are fully mixed together at the preheaters of C1, C2 and C3 or a kiln tail smoke exhaust pipeline and kiln tail smoke, and catalyze SO at the high temperature of the preheaters of C1, C2, C3 or the kiln tail smoke exhaust pipeline2Molecule, O2Molecule, CaCO3The powder and CaO powder are subjected to chemical reaction to generate stable CaSO4Microparticles; generated CaSO4The particles are collected at a dust collector and enter a raw material warehouse, and finally, sulphoaluminate cement clinker is formed in the rotary kiln. The added metal compound accounts for 5-80ppm of the input amount of the cement kiln, and basically has no influence on cement production.
The invention has the beneficial effects that:
1. the invention adopts CaCO carried by kiln tail flue gas3The powder and CaO powder are used as a desulfurizer, so that the desulfurization cost can be greatly reduced.
2. The invention does not generate solid waste to the outside, and the generated desulfurization product CaSO4The particles can be directly used as raw materials, and in the process of preparing cement by using clinker, the particles not only have no influence on the quality of the cement, but also improve the early strength of the cement.
3. The invention does not need to consume a large amount of water resources and worry about the white smoke phenomenon of the kiln tail chimney.
4. The invention adopts the catalytic desulfurization technology, improves the desulfurization effect by adding the catalyst, has high desulfurization reaction efficiency and can realize desulfurization of more than 98 percent.
5. The invention adopts low-cost metal compound as the catalyst for desulfurization, although a certain amount of catalyst needs to be consumed, the early investment cost can be greatly reduced, meanwhile, the risks of operation blockage and the like are avoided, and the overall economy is better.
6. At present, high-quality limestone resources are more and more scarce, and high-sulfur limestone ore can be used by the method, so that the operation cost of enterprises is greatly reduced, and national mineral resources are saved.
7. The catalytic desulfurization effect can reach more than 98 percent; by controlling the adding amount of the catalyst, the exhaust emission can be stabilized at 100mg/m3In the following, the SO is greatly reduced2The discharge amount is increased, and the domestic environment quality is improved.
8. In the operation process, the method has no influence on the prior cement clinker and a cement production system, can realize large-scale desulfurization only by a small amount of field and equipment investment, and has good economical efficiency.
Detailed Description
The present invention is further illustrated by the following examples.
Example 1
In 2500t/d cement plant, the sulfur content of high-sulfur ore is 0.4-0.9%, and the maximum SO content of flue gas is obtained during the stop period of vertical mill2Discharge 1278mg/Nm3After adopting the scheme of the embodiment, wherein SO2The discharge amount is stabilized at 90-150mg/m3And the emission standard of the country is reached.
The scheme of the embodiment specifically comprises the following steps:
(1) selecting micron-sized manganese ore powder (mainly containing manganese carbonate and manganese oxide) and water according to the mass ratio of 5:100, and preparing a manganese metal-containing catalytic aqueous solution through a stirring tank;
(2) spraying the raw material to a C1 preheater at the position of a belt chute of a raw material feeding system according to the spraying amount of 0.1-0.3 ton/h, and quickly mixing the sprayed catalytic water agent with flue gas and the raw material at the position of a C1 preheater;
(3) in the C1, C2 and C3 preheaters, each 1mm3About 1 × 10 is present in the flue gas of (1)6Micron-sized metal catalystPellets, about 1.4 × 1012A SO2Fine particles and about 5.5 × 108A H2O and billions of CaCO3Particles, at the high temperature of the flue gas of 300-600 ℃, the related molecules and particles rapidly perform Brownian motion, SO2Under the action of catalyst, converting into SO3And rapid mixing with CaCO3The particles combine to form stable CaSO4Microparticles;
（4）CaSO4the particles are collected at the dust collector and enter a raw material system, and finally enter a kiln system to be converted into clinker to be discharged.
Example 2
In a 4000t/d cement plant, high-sulfur ores, having a sulfur content of 0.8% to 1.4%, have to be used due to limestone mine factors, in which SO is contained in flue gas during the stand mill stop2Discharge of 1100-1500 mg/Nm3Sometimes up to 2200mg/Nm3After adopting the scheme of the embodiment, wherein SO2The discharge amount is stabilized at 30-80mg/m3Less than 100mg/m3National emission standards.
The scheme of the embodiment specifically comprises the following steps:
(1) preparing a catalyst solution by using copper sulfate, a 20% ammonia water solution and water according to a mass ratio of 2:200: 800;
(2) 2 injection points are respectively arranged on a discharge chute of a raw material kiln entering system and a C1 preheater of a cement kiln system, wherein the discharge chute is provided with 2 nozzles, and 4 nozzles are annularly and uniformly distributed at the C1 preheater;
(3) the catalyst solution is respectively sprayed into the 2 spraying points according to 0.5 ton/h and 1.2 ton/h, the catalyst sprayed into the raw material is finally mixed with the kiln tail flue gas at the preheaters of C1, C2 and C3, and the CaCO in the catalyst and the kiln tail flue gas is realized3Mixing with CaO powder, and catalyzing SO at high temperature (generally over 100 deg.C)2Molecule, O2Molecule, CaCO3The powder and CaO powder are subjected to chemical reaction to generate stable CaSO4Microparticles;
(4) generated CaSO4And the particles are collected by a dust collector and then enter the cement clinker system again.
No solid waste is generated in the whole process, wherein SO2The discharge amount is stabilized at 30-80mg/m3Less than 100mg/m3。
Example 3
4000t/d cement plant, which adopts high-sulfur ore with the sulfur content of 0.9-1.5%, wherein SO in flue gas during the stop period of the vertical mill2Discharge of 1100-1900 mg/Nm3After adopting the scheme of the embodiment, wherein SO2The discharge capacity is stabilized at 100-180mg/m3Less than 200mg/m3And the national emission standard is reached.
The scheme of the embodiment is different from that of the embodiment 1: adding iron ore (main components such as Fe2O3 and siderite FeCO 3) and manganese ore (mainly containing manganese carbonate and manganese oxide) and raw materials into a batching system of a raw material warehouse according to the ratio of 1:1:98, and grinding the iron ore and the manganese ore into catalytic powder while grinding the raw materials into raw material powder at a raw material grinding part; in the grinding process, kiln tail flue gas can assist in removing part of sulfur through a raw material mill; simultaneously, the raw material is also used as a catalyst to catalyze SO after being put into a kiln2Molecule, O2Molecule, CaCO3The powder and CaO powder are subjected to chemical reaction to generate stable CaSO4And (3) microparticles.
Various modifications and variations of the present invention may be made by those skilled in the art, and they are also within the scope of the present invention provided they are within the scope of the claims of the present invention and their equivalents.
What is not described in detail in the specification is prior art that is well known to those skilled in the art.
Claims (9)
1. A method for using high-sulfur raw materials for a cement kiln utilizes a raw material preparation system, a raw material warehouse, a raw material kiln entering system, a preheater system, a kiln tail smoke exhaust channel and dust collector equipment of the existing dry-process cement kiln, and is characterized by specifically comprising the following steps of:
(1) preparing catalytic powder or catalytic aqueous solution by using a metal compound, wherein the metal compound is a compound of manganese, iron, copper or zinc;
(2) spraying or scattering the catalytic powder or catalytic water agent obtained in the step (1) on raw material preparation system or raw material warehouse or raw material kiln system or raw material of a preheater system of C1, C2 and C3 or raw material of a smoke exhaust channel at the tail of a kiln or raw material or smoke powder particles;
(3) the catalytic powder or catalytic water agent sprayed or scattered in the raw materials or the raw materials is finally mixed with the kiln tail flue gas at the preheaters of C1, C2 and C3 to realize the mixing of the catalytic powder or catalytic water agent and CaCO in the kiln tail flue gas3Mixing with CaO powder particles, and catalyzing SO at high temperature2Molecule, O2Molecule, CaCO3The powder and CaO powder are subjected to chemical reaction to generate stable CaSO4Microparticles;
(4) generated CaSO4The particles are collected by a dust collector and then enter the cement kiln again to finally become cement clinker.
2. The method of using a high sulfur feedstock in a cement kiln as recited in claim 1, wherein: in the step (1), the metal compound is an oxide or a metal salt.
3. The method of using high sulfur feedstock in a cement kiln according to claim 2, wherein: the metal salt is soluble metal salt.
4. The method of using high sulfur feedstock for a cement kiln as claimed in claim 1 or 2, wherein: in the step (1), the metal compound is metal compound ore, and is prepared with the raw material together at a raw material warehouse and a raw material preparation system, and is ground into metal compound powder in a raw material mill.
5. The method of using high sulfur feedstock for a cement kiln as claimed in claim 1 or 2, wherein: in the step (1), ammonia or amine is added into the catalytic water agent; or in the step (2), separately injecting ammonia or amine.
6. The method of using high sulfur feedstock for a cement kiln as claimed in claim 1 or 2, wherein: in the step (1), a surfactant and/or an aggregating agent are added into the catalytic water agent; or in the step (2), the surfactant and/or the agglomerating agent are sprayed in separately.
7. The method of using high sulfur feedstock for a cement kiln as claimed in claim 1 or 2, wherein: in the step (2), the raw material preparation system refers to a whole process of preparing raw materials from limestone raw materials, and comprises a raw material warehouse, a conveying belt, a raw material mill and a raw material warehouse entry system; the raw material kiln feeding system is equipment in the whole process from raw material discharged from a raw material warehouse to raw material feeding into a preheater system, and comprises a material conveying belt, a material conveying hoister and a chute; the kiln tail smoke exhaust channel refers to a pipeline and equipment through which kiln tail smoke flows from the preheater to the kiln tail dust collector.
8. The method of using high sulfur feedstock for a cement kiln as claimed in claim 1 or 2, wherein: in the step (2), the dosage of the catalytic powder or the catalytic water agent is prepared according to the sulfur content of the high-sulfur ore, the sulfur content of the kiln tail flue gas raw material and the kiln feeding amount of the raw material.
9. The method of using high sulfur feedstock for a cement kiln as claimed in claim 1 or 2, wherein: in the step (2), the spraying or scattering points are arranged on one or more than two points and are arranged on a raw material preparation system, a raw material warehouse, a raw material kiln entering system, a preheater system or a kiln tail smoke and smoke exhaust channel.
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Cited By (1)
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| CN111841322A (en) * | 2020-07-29 | 2020-10-30 | 湖南萃智环保科技有限公司 | Denitration and discharge method for cement kiln |
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| CN111841322A (en) * | 2020-07-29 | 2020-10-30 | 湖南萃智环保科技有限公司 | Denitration and discharge method for cement kiln |
| CN111841322B (en) * | 2020-07-29 | 2022-08-19 | 安徽萃智环保科技有限公司 | Denitration and discharge method for cement kiln |
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