CN106565116B - It is a kind of to absorb SO in cement kiln flue gas using diatomite/calcium based compound additive2Method - Google Patents

It is a kind of to absorb SO in cement kiln flue gas using diatomite/calcium based compound additive2Method Download PDF

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CN106565116B
CN106565116B CN201610996569.7A CN201610996569A CN106565116B CN 106565116 B CN106565116 B CN 106565116B CN 201610996569 A CN201610996569 A CN 201610996569A CN 106565116 B CN106565116 B CN 106565116B
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diatomite
gas
absorb
cement
cao
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CN106565116A (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)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Treating Waste Gases (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

It is a kind of to absorb SO in cement kiln flue gas using diatomite/calcium based compound additive2Method, belong to industrial furnace smoke process field.The present invention dries for 24 hours at a temperature of diatomite is placed in 60-105 DEG C first；Then by the diatomite of 10-15%wt, the CaO of 7%wt or Ca (OH)2It is mixed with the cement slurry of 78%-83%wt, at 300-500 DEG C, SO is passed through into mixture2Gas utilizes diatomite and CaO or Ca (OH)2Absorb SO2Gas is to achieve the purpose that desulfurization.The diatomite that the present invention uses has characteristic that is porous and adsorbing by force, can be cement slurry and CaO or Ca (OH)2Absorb SO2Gas provides more reaction compartments and place.The diatomite and CaO or Ca (OH) of addition2It is close with the ingredient of cement raw material, therefore will not influence the final mineral composition and performance of clinker.Present invention process is simple, and adsorbent material source is wide, and desulfuration efficiency is high.

Description

It is a kind of to absorb SO in cement kiln flue gas using diatomite/calcium based compound additive2's Method
Technical field
The invention belongs to industrial furnace smoke process fields, and in particular to a kind of to utilize diatomite/calcium based compound additive Absorb SO in cement kiln flue gas2Method.
Background technique
SO in cement industry kiln furnace exhaust gas2It is one of atmosphere pollution, will cause a series of environmental problems such as acid rain, greatly Most cement production enterprises all suffer from SO2Emission reduction problem.Modern cement production enterprise generally uses new dry cement production technology, water Mud raw material are completed to enter in kiln after decomposing in preheater and are burnt into.Due to containing a large amount of sulfur-containing compound in raw material and fuel, A large amount of SO can be generated during causing material to decompose with fuel combustion2Gas is discharged into air and causes serious atmosphere Pollution.
The desulfurization of cement industry at this stage mainly has cement industry from emission reduction (emission reduction) technology and additional SO2It is de- Except (secondary emission reduction) technology.Cement industry emission-reduction technology is mainly that the lime stone in raw material is utilized to absorb SO2Reach the mesh of emission reduction , preheating decomposition furnace is the ideal place that desulphurization reaction occurs, there is a large amount of activity CaO in dore furnace, from thermodynamics and For aerodynamic point, within the temperature range of 800-950 DEG C, CaO absorbs SO2Reaction can carry out well, but gas group It has a certain impact at ingredient to desulfurization effect, therefore from the point of view of technological angle, needing to control the combustion atmosphere in kiln could reach To reduction SO2The purpose of discharge.Additional 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 mostly exists that desulfuration efficiency is low, equipment investment is big or operation at The problems such as this is high, so the SO of quality coal in cement kiln systems2Emission reduction problem needs further to study and improve.
It is existing studies have shown that cement kiln SO2Discharge mainly in raw material pyrite and marcasite (the two is FeS2) and some single sulphur compounds (such as FeS) it is related, oxidation will occur at 500-600 DEG C and generate for these low price sulphides SO2Gas, reaction occur mainly in second level cylinder, the SO released2Gas a part is absorbed by alkaline material, and another part is then It is discharged into atmosphere.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 Desulfurization effect be better than CaCO3, CaCO3In the case where temperature is lower than 600 DEG C, if the not effect of water, desulfurization effect is very Difference.Due to the CaCO in cement raw material lime stone3Just start to decompose at 700 DEG C to generate CaO, therefore one, the two of preheater SO in grade cyclone cylinder2Removal efficiency it is very low, so as to cause SO2That discharges is exceeded.
Summary of the invention
It is an object of the invention to propose that a kind of utilization diatomite/calcium based compound additive absorbs SO in cement kiln flue gas2 Method, the SO of cement kiln can be effectively reduced2Gas emissions, to reduce atmosphere pollution.Present invention process is simple, takes off Sulphur efficiency is up to 30-65%.
It is a kind of to absorb SO in cement kiln flue gas using diatomite/calcium based compound additive2Method, which is characterized in that packet It includes following steps: being dried for 24 hours at a temperature of diatomite is placed in 60-105 DEG C first；Then by the diatomite of 10-15%wt, 7% The alkaline material of wt is mixed with the cement slurry of 78%-83%wt, and alkaline material is CaO and Ca (OH)2One of both；Then Adequately grinding, is uniformly mixed cement slurry with diatomite, alkaline material；Finally at a high temperature of 300-500 DEG C, to diatom SO is passed through in the mixture of soil, alkaline material and cement slurry2Gas absorbs SO using diatomite and alkaline material2Gas is to reach To the purpose of desulfurization.
The beneficial effects of the present invention are:
It (1) can be cement slurry and CaO or Ca (OH) using characteristic that is diatomite porous and adsorbing by force2Absorb SO2Gas Body provides more reaction compartments and place, to improve SO2Absorptivity.
(2) the method for the present invention is without being transformed existing cement kiln, and cost of investment is low and easy to operate, adsorption material Expect from a wealth of sources, CaO or Ca (OH) in practical application2It can be provided by industrial residues such as carbide slags, to reach the mesh of waste utilization 's.
(3) addition diatomite will not have an impact the composition of cement raw material, it is ensured that and the normal operation of cement kiln is right The performance of clinker will not generate adverse effect.
Using 10-15%wt diatomite, 7%wtCaO or Ca (OH)2With the mixed raw material of 78%-83%wt cement slurry When being tested, 300-500 DEG C at a temperature of, mixture is for SO2The removal efficiency of gas reaches 30-65%.
Specific embodiment
Below with reference to embodiment, the invention will be further described, but the present invention is not limited to following embodiments.
Embodiment 1
At a temperature of diatomite is placed in 95 DEG C first it is dry for 24 hours, then take 15%wt (3.2g) diatomite, 7%wtCaO and 78%wt silicate cement raw material (fineness is that 0.08mm tails over 14%) is ground, and material to be mixed is added after mixing In the tube furnace for being 3cm to diameter.Then O is passed through into mixture2、N2And SO2(800ppm) mixed gas, O2And N2The two Volume ratio is 1:4, is that 0.5L/min is measured mixed finally under the conditions of 400 DEG C of temperature by the gas flow inside material Condensation material is for SO2The removal efficiency of gas is 40%.
Embodiment 2
At a temperature of diatomite is placed in 95 DEG C first it is dry for 24 hours, then take 15%wt (3.2g) diatomite, 7%wtCaO and 78%wt silicate cement raw material (fineness is that 0.08mm tails over 14%) is ground, and material to be mixed is added after mixing In the tube furnace for being 3cm to diameter.Then O is passed through into mixture2、N2And SO2(800ppm) mixed gas, O2And N2The two Volume ratio is 1:4, is that 0.5L/min is measured mixed finally under the conditions of 500 DEG C of temperature by the gas flow inside material Condensation material is for SO2The removal efficiency of gas is 57%.
Embodiment 3
Drying for 24 hours, then takes 10%wt (3g) diatomite, 7%wtCa (OH) at a temperature of diatomite is placed in 95 DEG C first2 It is ground with 83%wt silicate cement raw material (fineness is that 0.08mm tails over 14%), material to be mixed is added after mixing In the tube furnace for being 3cm to diameter.Then O is passed through into mixture2、N2And SO2(800ppm) mixed gas, O2And N2The two Volume ratio is 1:4, is that 0.5L/min measures mixing finally under the conditions of 500 DEG C of temperature by the gas flow inside material Material is for SO2The removal efficiency of gas is 51%.
Embodiment 4
At a temperature of diatomite is placed in 95 DEG C first it is dry for 24 hours, then take 10%wt (3g) diatomite, 7%wtCaO and 83%wt silicate cement raw material (fineness is that 0.08mm tails over 14%) is ground, and material to be mixed is added after mixing In the tube furnace for being 3cm to diameter.Then O is passed through into mixture2、N2And SO2(800ppm) mixed gas, O2And N2The two Volume ratio is 1:4, is that 0.5L/min is measured mixed finally under the conditions of 500 DEG C of temperature by the gas flow inside material Condensation material is for SO2The removal efficiency of gas is 53%.
Embodiment 5
Drying for 24 hours, then takes 15%wt (3.2g) diatomite, 7%wtCa at a temperature of diatomite is placed in 95 DEG C first (OH)2It is ground with 78%wt silicate cement raw material (fineness is that 0.08mm tails over 14%), material to be mixed is uniformly mixed It is added in the tube furnace that diameter is 3cm afterwards.Then O is passed through into mixture2、N2And SO2(800ppm) mixed gas, O2With N2The volume ratio of the two is 1:4, is 0.5L/min by the gas flow inside material, finally under the conditions of 500 DEG C of temperature, Mixing material is measured for SO2The removal efficiency of gas is 62%.
Embodiment 6
Drying for 24 hours, then takes 10%wt (3g) diatomite, 7%wtCa (OH) at a temperature of diatomite is placed in 95 DEG C first2 It is ground with 83%wt silicate cement raw material (fineness is that 0.08mm tails over 14%), material to be mixed is added after mixing In the tube furnace for being 3cm to diameter.Then O is passed through into mixture2、N2And SO2(800ppm) mixed gas, O2And N2The two Volume ratio is 1:4, is that 0.5L/min measures mixing finally under the conditions of 300 DEG C of temperature by the gas flow inside material Material is for SO2The removal efficiency of gas is 31%.
By above-mentioned experimental data it is found that diatomite/calcium based additives inhale cement slurry at a temperature of 300-500 DEG C Receive SO2Beneficial, in addition, ingredient of the diatomite ingredient very close to portland cement raw material, diatomite/calcium based compound additive is not The composition of clinker can be impacted, and diatomite abundance.In general, diatomite/calcium based compound additive With good economic efficiency and environmental benefit.

Claims (2)

1. a kind of absorb SO in cement kiln flue gas using diatomite/calcium based compound additive2Method, which is characterized in that including with Lower step: it is dried for 24 hours at a temperature of diatomite is placed in 60-105 DEG C first；Then by the diatomite of 10-15%wt, 7%wt Alkaline material is mixed with the cement slurry of 78%-83%wt, and alkaline material is CaO and Ca (OH)2One of both；Then adequately Grinding, is uniformly mixed cement slurry with diatomite, alkaline material；Finally 300-500 DEG C at a temperature of, using diatomite and Alkaline material absorbs SO2Gas.
2. a kind of utilization diatomite/calcium based compound additive according to claim 1 absorbs SO in cement kiln flue gas2Side Method, it is characterised in that: 300-500 DEG C at a temperature of, mixture 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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CN109569254B (en) * 2018-11-28 2021-12-21 苏州拓纳超细粉体有限公司 Calcium carbonate powder for wet desulphurization and preparation method of calcium carbonate powder for wet desulphurization

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

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