CN106565116A - Method for utilizing kieselguhr/calcium-based composite additive for absorbing SO2 in cement kiln smoke - Google Patents

Method for utilizing kieselguhr/calcium-based composite additive for absorbing SO2 in cement kiln smoke Download PDF

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CN106565116A
CN106565116A CN201610996569.7A CN201610996569A CN106565116A CN 106565116 A CN106565116 A CN 106565116A CN 201610996569 A CN201610996569 A CN 201610996569A CN 106565116 A CN106565116 A CN 106565116A
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gas
diatomite
kieselguhr
cement
cao
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CN201610996569.7A
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CN106565116B (en
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崔素萍
赵洪强
王亚丽
兰明章
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Beijing University of Technology
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Beijing University of Technology
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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
    • C04B7/02—Portland cement
    • C04B7/06—Portland cement using alkaline raw materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/48—Sulfur compounds
    • B01D53/50—Sulfur oxides
    • B01D53/501—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/602—Oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention discloses a method for utilizing a kieselguhr/calcium-based composite additive for absorbing SO2 in cement kiln smoke, and belongs to the field of industrial kiln smoke treatment. According to the method, the kieselguhr is dried for 24 h at the temperature ranging from 60 DEG C to 105 DEG C; then, 10wt-15%wt of kieselguhr, 7%wt of CaO or Ca(OH)2 and 78%wt-83%wt of cement raw materials are mixed, the mixture is inflated with SO2 gas at the temperature ranging from 300 DEG C to 500 DEG C, the kieselguhr and the CaO or the Ca(OH)2 are utilized for absorbing SO2 gas so as to achieve the purpose of desulfurization. The kieselguhr adopted in the method has the characters of porousness and strong adsorption, and more reaction spaces and places can be provided for the cement raw materials and the CaO or the Ca(OH)2 for absorbing SO2 gas. The added kieselguhr and the added CaO or Ca(OH)2 are close to the cement raw materials in component, and therefore the final mineral composition and performance of cement clinker cannot be affected. The technology is simple, the adsorption material source is wide, and the desulphurization efficiency is high.

Description

One kind absorbs SO in cement kiln flue gas using diatomite/calcium based compound additive2's Method
Technical field
The invention belongs to industrial furnace smoke process field, and in particular to one kind utilizes diatomite/calcium based compound additive Absorb SO in cement kiln flue gas2Method.
Background technology
SO in cement industry kiln furnace exhaust gas2It is one of atmosphere pollution, the series of environmental problems such as acid rain can be caused, greatly Most cement production enterprises all suffer from SO2Reduction of discharging problem.Modern cement production enterprise has commonly used new dry cement production technology, water Mud raw material are entered after completing to decompose in preheater and burnt till in kiln.Due to containing substantial amounts of sulfur-containing compound in raw material and fuel, Material is caused to produce substantial amounts of SO during decomposing with fuel combustion2Gas, enters and cause in air serious air Pollution.
The desulfurization of cement industry at this stage mainly has cement industry from reduction of discharging (once reducing discharging) technology and extra SO2It is de- Except (secondary reduction of discharging) technology.The lime stone that cement industry emission-reduction technology is mainly used in raw material absorbs SO2Reach the mesh of reduction of discharging , preheating decomposition furnace be desulphurization reaction occur ideal place, there is substantial amounts of active CaO in dore furnace, from thermodynamics with For aerodynamic point, within the temperature range of 800-950 DEG C, CaO absorbs SO2Reaction can carry out well, but gas group Desulfurized effect is had a certain impact into composition, therefore from the point of view of technological angle, needs the combustion atmosphere controlled in kiln to reach To reduction SO2The purpose of discharge.Extra SO2Emission-reduction technology has desulfurization by dry method, Wet Flue Gas Desulfurization Technique, semi-dry desulphurization skill Art and compound desulfurization technology etc., but existing desulfurization technology is mostly present, and desulfuration efficiency is low, equipment investment big or runs into The problems such as this is high, so the SO of quality coal in cement kiln systems2Reduction of discharging problem needs further research and improves.
Existing research shows, the SO of cement kiln2Discharge mainly with raw material in pyrite and marcasite (both are FeS2) and some single sulphur compounds (such as FeS) it is relevant, these low price sulphides will occur at 500-600 DEG C oxidation generate SO2Gas, reaction occurs mainly in two grades of cylinders, the SO for discharging2A gas part is absorbed by alkaline material, and another part is then In being discharged into air.Document《Formation and techniques for control of sulfur dioxide and other sulfur compounds in Portland cement kiln systems》In show CaO and Ca (OH)2 Desulfurized effect be better than CaCO3, CaCO3In the case where temperature is less than 600 DEG C, if the effect without water, desulfurized effect is very Difference.Due to the CaCO in cement raw material lime stone3Just start to decompose at 700 DEG C and generate CaO, therefore in preheater one, two SO in level cyclone cylinder2Removal efficiency it is very low, so as to cause SO2That what is discharged is exceeded.
The content of the invention
It is an object of the invention to propose a kind of using SO in diatomite/calcium based compound additive absorption cement kiln flue gas2 Method, the SO of cement kiln can be effectively reduced2Gas emissions, so as to reduce atmosphere pollution.Present invention process is simple, takes off Sulphur efficiency is up to 30-65%.
One kind absorbs SO in cement kiln flue gas using diatomite/calcium based compound additive2Method, it is characterised in that bag Include following steps：24h is dried at a temperature of first diatomite being placed in into 60-105 DEG C；Then by the diatomite of 10-15%wt, 7% The alkaline material of wt mixes with the cement slurry of 78%-83%wt, and alkaline material is CaO and Ca (OH)2One of both；Then fill The grinding for dividing, makes cement slurry be well mixed with diatomite, alkaline material；Finally at a high temperature of 300-500 DEG C, to diatom SO is passed through in the compound of soil, alkaline material and cement slurry2Gas, using diatomite and alkaline material SO is absorbed2Gas is reaching To the purpose of desulfurization.
The invention has the beneficial effects as follows：
(1) can be cement slurry and CaO or Ca (OH) using the characteristic of diatomite porous and strong absorption2Absorb SO2Gas Body provides more reaction compartments and place, so as to improve SO2Absorptivity.
(2), without the need for transforming existing cement kiln, cost of investment is low and simple to operate, adsorption material for the inventive method Material wide material sources, CaO or Ca (OH) in practical application2Can be provided by industrial residues such as carbide slags, to reach the mesh of twice laid 's.
(3) adding diatomite will not produce impact to the composition of cement raw material, it is ensured that the normal operation of cement kiln, right The performance of clinker will not also produce harmful effect.
Using 10-15%wt diatomite, 7%wtCaO or Ca (OH)2With the mixed material of 78%-83%wt cement slurries When being tested, at a temperature of 300-500 DEG C, compound is for SO2The removal efficiency of gas reaches 30-65%.
Specific embodiment
With reference to embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
24h is dried at a temperature of first diatomite being placed in into 95 DEG C, then take 15%wt (3.2g) diatomite, 7%wtCaO and 78%wt silicate cement raw materials (fineness tails over 14% for 0.08mm) are ground, and material to be mixed is added to after being well mixed In the tube furnace of a diameter of 3cm.Then it is passed through O in compound2、N2And SO2(800ppm) mixed gas, O2And N2The body of the two Product is than being 1:4, it is 0.5L/min by the gas flow inside material, finally under 400 DEG C of temperature conditionss, measure mixing material Material is for SO2The removal efficiency of gas is 40%.
Embodiment 2
24h is dried at a temperature of first diatomite being placed in into 95 DEG C, then take 15%wt (3.2g) diatomite, 7%wtCaO and 78%wt silicate cement raw materials (fineness tails over 14% for 0.08mm) are ground, and material to be mixed is added to after being well mixed In the tube furnace of a diameter of 3cm.Then it is passed through O in compound2、N2And SO2(800ppm) mixed gas, O2And N2The body of the two Product is than being 1:4, it is 0.5L/min by the gas flow inside material, finally under 500 DEG C of temperature conditionss, measure mixing material Material is for SO2The removal efficiency of gas is 57%.
Embodiment 3
24h is dried at a temperature of first diatomite being placed in into 95 DEG C, 10%wt (3g) diatomite, 7%wtCa (OH) is then taken2 It is ground with 83%wt silicate cement raw materials (fineness tails over 14% for 0.08mm), material to be mixed is added after being well mixed To in the tube furnace of a diameter of 3cm.Then it is passed through O in compound2、N2And SO2(800ppm) mixed gas, O2And N2The two Volume ratio is 1:4, it is 0.5L/min by the gas flow inside material, finally under 500 DEG C of temperature conditionss, measure mixing Material is for SO2The removal efficiency of gas is 51%.
Embodiment 4
24h is dried at a temperature of first diatomite being placed in into 95 DEG C, then take 10%wt (3g) diatomite, 7%wtCaO and 83%wt silicate cement raw materials (fineness tails over 14% for 0.08mm) are ground, and material to be mixed is added to after being well mixed In the tube furnace of a diameter of 3cm.Then it is passed through O in compound2、N2And SO2(800ppm) mixed gas, O2And N2The body of the two Product is than being 1:4, it is 0.5L/min by the gas flow inside material, finally under 500 DEG C of temperature conditionss, measure mixing material Material is for SO2The removal efficiency of gas is 53%.
Embodiment 5
24h is dried at a temperature of first diatomite being placed in into 95 DEG C, 15%wt (3.2g) diatomite, 7%wtCa is then taken (OH)2It is ground with 78%wt silicate cement raw materials (fineness tails over 14% for 0.08mm), material to be mixed is well mixed In being added to the tube furnace of a diameter of 3cm afterwards.Then it is passed through O in compound2、N2And SO2(800ppm) mixed gas, O2And N2 The volume ratio of the two is 1:4, it is 0.5L/min by the gas flow inside material, finally under 500 DEG C of temperature conditionss, survey Mixing material is obtained for SO2The removal efficiency of gas is 62%.
Embodiment 6
24h is dried at a temperature of first diatomite being placed in into 95 DEG C, 10%wt (3g) diatomite, 7%wtCa (OH) is then taken2 It is ground with 83%wt silicate cement raw materials (fineness tails over 14% for 0.08mm), material to be mixed is added after being well mixed To in the tube furnace of a diameter of 3cm.Then it is passed through O in compound2、N2And SO2(800ppm) mixed gas, O2And N2The two Volume ratio is 1:4, it is 0.5L/min by the gas flow inside material, finally under 300 DEG C of temperature conditionss, measure mixing Material is for SO2The removal efficiency of gas is 31%.
From above-mentioned experimental data, diatomite/calcium based additives absorb for cement slurry at a temperature of 300-500 DEG C SO2Beneficial, additionally, the composition of diatomite composition closely portland cement raw material, diatomite/calcium based compound additive will not The composition of clinker is impacted, and diatomite abundance.In general, diatomite/calcium based compound additive tool There is good economic benefit and environmental benefit.

Claims (2)

1. it is a kind of to absorb SO in cement kiln flue gas using diatomite/calcium based compound additive2Method, it is characterised in that include with Lower step：24h is dried at a temperature of first diatomite being placed in into 60-105 DEG C；Then by the diatomite of 10-15%wt, 7%wt Alkaline material mixes with the cement slurry of 78%-83%wt, and alkaline material is CaO and Ca (OH)2One of both；Then it is sufficient Grinding, makes cement slurry be well mixed with diatomite, alkaline material；It is last at a temperature of 300-500 DEG C, using diatomite and Alkaline material absorbs SO2Gas.
2. the one kind according to right 1 absorbs SO in cement kiln flue gas using diatomite/calcium based compound additive2Method, its It is characterised by：At a temperature of 300-500 DEG C, compound is to SO2The removal efficiency of gas reaches 30-65%.
CN201610996569.7A 2016-11-13 2016-11-13 It is a kind of to absorb SO in cement kiln flue gas using diatomite/calcium based compound additive2Method Active CN106565116B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109569254A (en) * 2018-11-28 2019-04-05 苏州拓纳超细粉体有限公司 Wet desulphurization calcium carbonate stone powder and wet desulphurization calcium carbonate stone powder preparation method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101337684A (en) * 2008-08-11 2009-01-07 昆明理工大学 Method for recovering sulfur and co-producing calcium carbonate from desulphurization gypsum
CN101462698A (en) * 2009-01-13 2009-06-24 南京师范大学 Industrial method for cyclic utilization of ironmaking production desulfurized gypsum and blast furnace gas
CN102489131A (en) * 2011-11-21 2012-06-13 广东电网公司电力科学研究院 Preparation method of wet desulphurization absorbent for flue gas from coal fired boiler

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101337684A (en) * 2008-08-11 2009-01-07 昆明理工大学 Method for recovering sulfur and co-producing calcium carbonate from desulphurization gypsum
CN101462698A (en) * 2009-01-13 2009-06-24 南京师范大学 Industrial method for cyclic utilization of ironmaking production desulfurized gypsum and blast furnace gas
CN102489131A (en) * 2011-11-21 2012-06-13 广东电网公司电力科学研究院 Preparation method of wet desulphurization absorbent for flue gas from coal fired boiler

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109569254A (en) * 2018-11-28 2019-04-05 苏州拓纳超细粉体有限公司 Wet desulphurization calcium carbonate stone powder and wet desulphurization calcium carbonate stone powder preparation method

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