CN108079776A - A kind of new dry process rotary kiln catalytic desulfurizing agent and its preparation and application - Google Patents

A kind of new dry process rotary kiln catalytic desulfurizing agent and its preparation and application Download PDF

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Publication number
CN108079776A
CN108079776A CN201711190438.0A CN201711190438A CN108079776A CN 108079776 A CN108079776 A CN 108079776A CN 201711190438 A CN201711190438 A CN 201711190438A CN 108079776 A CN108079776 A CN 108079776A
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aqua
desulfurizing agent
rotary kiln
component
dry process
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CN201711190438.0A
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孙晋国
王朋
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Zaozhuang Yihong Environmental Protection Technology Co., Ltd.
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Beijing Greenstone Environmental Protection Science And Technology Co Ltd
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    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • 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
    • B01D53/502—Sulfur oxides by treating the gases with a solution or a suspension of an alkali or earth-alkali or ammonium compound characterised by a specific solution or suspension
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/78—Liquid phase processes with gas-liquid contact
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/77—Liquid phase processes
    • B01D53/79—Injecting reactants
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8603—Removing sulfur compounds
    • B01D53/8609—Sulfur oxides
    • 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
    • C04B7/364—Avoiding environmental pollution during cement-manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/10—Oxidants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/20—Reductants
    • B01D2251/206—Ammonium compounds
    • B01D2251/2062—Ammonia
    • 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

Abstract

The invention discloses a kind of new dry process rotary kiln catalytic desulfurizing agent and its preparation and application, provide a kind of catalytic desulfurizing agent for reducing cement production enterprise SO2 emissions.Comprising pulvis and aqua two parts, wherein, the mass percent of pulvis each component is calcium carbonate：45~65%, calcium oxide:28~45%, iron oxide:0.1~1%, magnesia:1~6.5%, barium carbonate:0.5~1.5%, rare element compound:1~5%, silica:3 5.5%, surplus is dolomite, the sum of fluorite, each component is 100%.By measuring：The utility model dry method kiln mix that weight ratio is raw meal quality outside with desulphurization denitration complexing agent 0.10%~1.50%, can emission reduction SO2 >=90%, SO2 discharge capacity≤100mg/m3 when aqua dosage is 1.0~3.0m3/h.

Description

A kind of new dry process rotary kiln catalytic desulfurizing agent and its preparation and application
Technical field
The present invention relates to environmental protection and energy saving fields, and in particular to a kind of dry-process cement rotary kiln desulfurizing agent.
Background technology
As stablizing for Chinese national economy is fast-developing, cement industry is developed on an unprecedented scale, and China also becomes when it The cement big country having nothing to be ashamed of.Therewith, the object that the pollution problem of cement industry becomes country and social level is paid close attention to.2013 Year, State Ministry of Environmental Protection can be revised with State Administration of Quality Supervision, Inspection and Quarantine's issue《Cement industry atmosphere pollutants emission standards》（GB-4915- 2013）, which has significantly cut down the discharge Limited Doses of the pollutants such as cement producing line particulate matter, nitrogen oxides, sulfur dioxide. The standard provides that sulfide in flue gas discharge Limited Doses are 100mg/m3.The discharge environmental pollution of sulfur dioxide is even more serious, Therefore, cement production enterprise SO2 emissions are reduced, it is extremely urgent, it is very urgent.
At present, market desulfurizing agent and desulfurization technology species are various, and whether wet desulphurization, dry desulfurization or ammonia take off Sulphur, it is unsatisfactory in cost of investment, operating cost, desulfuration efficiency etc., exist simultaneously occur in system operation it is all More problems.Undoubtedly, new dry process rotary kiln exit gas desulphurization complexing of new generation is invented, it is necessary.
The content of the invention
The object of the present invention is to provide a kind of catalytic desulfurizing agents for reducing cement production enterprise SO2 emissions.For in realization Purpose is stated, the technical solution adopted by the present invention is：
A kind of new dry process rotary kiln catalytic desulfurizing agent, comprising pulvis and aqua two parts, wherein, the quality hundred of pulvis each component It is calcium carbonate to divide ratio：45~65%, calcium oxide:28~45%, iron oxide:0.1~1%, magnesia:1~6.5%, carbonic acid Barium:0.5~1.5%, rare element compound:1~5%, silica:3-5.5%, surplus is dolomite, fluorite, each group / and be 100%；
It is as follows that rare element compound each component accounts for total rare element total amount of compound mass percent：Manganese dioxide 70~ 80%th, titanium dioxide 15~20%, ceria 2~6%, 0 .5~5% of lithium hydroxide, oxidant：The sum of 1-3%, each component For 100%；Pulvis additive amount is the 0.1~1.5% of cement raw meal quality, and aqua is the reducing agent for being dissolved in water, and aqua dosage is 1.0~3.0m3/h.
The oxidizer composition is ammonium hydrogencarbonate and nitric acid ammonia.The reducing agent ingredient is NH3, concentration 3-6w%.
New dry process rotary kiln catalytic desulfurizing agent preparation method described in a kind of claim 1, preparation method step is as follows,
A, by each component by above-mentioned weight ratio dispensing, difference is successively in metered mixer；
B, mixture by deep processing is ground into powder material, is sufficiently mixed under batch mixer, obtains desulfurizing agent dry powder；
C, reducing agent and water are blent in proportion, is sufficiently mixed the water-soluble reducing agent for stirring to get homogeneous.
New dry process rotary kiln catalytic desulfurizing agent application method described in a kind of claim 1,
A, enter setting desulphurization denitration complexing agent bulk pot by kiln elevator, pass through the electron helical scale velometer under bulk pot Amount, is uniformly added into mash form in kiln elevator；Aqua adjusts flow by fluid flowmeter, and preheating is pumped to through conveying In device C2 uptake flues, sprayed through the atomization nozzle of flue, to ensure the atomizing effect of aqua；
B, desulfurization powder addition accounts for the 0.10%~1.50% of raw material weight, and aqua dosage is 1.0~3.0m3/h, depending on Sulfide emission amount and raw material feeding capacity give.
The formula that the utility model dry-process cement rotary kiln catalytic desulfurizing agent is combined using pulvis, aqua, raw material are easily obtained, cost Relatively low, component scientific matching can effectively cut down the pollutant emissions Limited Doses such as cement producing line sulfur dioxide.
By measuring：It is raw meal quality that the utility model dry method kiln mixes weight ratio outside with desulphurization denitration complexing agent 0.10%~1.50%, it, can emission reduction SO2 >=90%, SO2 discharge capacity≤100mg/ when aqua dosage is 1.0~3.0m3/h m3。
Specific embodiment
The present invention will be further described below.
To reduce the discharge of cement production enterprise SO2, the present invention proposes a kind of suitable for cement kiln catalytic desulfurizing agent, the desulfurization Agent is fed together with raw material in preheater, real through a series of physical reactions, chemical reaction under the action of high temperature in preheater Existing high-temperature fixed sulfur, so as to reduce SO2 discharges and not have any negative effect to the performance of clinker.
First, the technical solution adopted by the present invention.
A kind of cement kiln catalytic desulfurizing agent, comprising pulvis and aqua two parts, pulvis component includes calcium carbonate, oxidation Calcium, iron oxide, magnesia, barium carbonate, oxidant, dolomite, fluorite, rare element compound.The desulfurizing agent is given birth to cement Material is added in kiln together, to reduce SO2 concentration in cement kiln flue gas.
Wherein, the mass percent of each component is calcium carbonate：45~65%, calcium oxide:28~45%, iron oxide: 0 .1~1%, magnesia:1~6.5%, barium carbonate:0.5~1.5%, rare element compound:1~5%, silica: 3-5.5%, surplus is dolomite, the sum of fluorite, each component is 100%.
It is as follows that each rare element compound component, which accounts for total rare element total amount of compound mass percent,.Manganese dioxide 70~80%, titanium dioxide 15~20%, ceria 2~6%, lithium hydroxide 0.5~5%, oxidant：1-3%, oxidant Ingredient is that the sum of ammonium hydrogencarbonate and nitric acid ammonia, each component are 100%.
Desulfurization powder additive amount is 0 .1~1.5% of cement raw meal quality.Aqua be a kind of reducing agent for being dissolved in water, water Agent dosage is 1.0~3.0m3/h.Reducing agent ingredient is NH3, concentration 3-6%.
The action principle of above-mentioned technical proposal of the present invention is as described below.
（1）SO2 oxidation process:Under the action of desulfurizing agent, sulfur dioxide in flue gas (SO2) is quickly generated sulfur trioxide (SO3), SOx reactivities and desulfurization reaction rate are significantly improved.
Reaction equation：2SO2+O2=2SO3
(2) flue gas desulfurization course：SO3 is reacted with calcium hydroxide, calcium oxide, magnesia, iron oxide, barium carbonate in flue gas, generation Sulfate realizes flue gas high-efficiency desulfurization.Specific reaction equation is as follows.
CaO+SO3=CaSO4 Ca (OH) 2+SO3=CaSO4+H2O MgO+H2O=Mg (OH) 2 ↓
Mg (OH) 2+SO3=MgSO4 Fe2O3+3SO3=Fe2 (SO4) 3 BaCO3+SO3=BaSO4 ↓+CO2
(3) high-temperature fixed sulfur process：It is burnt till the stage in cement kiln, sulfate (CaSO4, BaSO4 etc.) and calcium oxide, aluminium oxide, oxygen Change iron etc. and solid phase reaction occurs, generate containing sulfur minerals, realize high-temperature fixed sulfur.
CaSO4+CaO+Al2O3→ (CaO·A12O3)·CaSO4
BaSO4+2CaSO4+CaO+Al2O3→ (CaO·BaO·A12O3)·2CaSO4
2nd, the specific preparation method of cement kiln catalytic desulfurizing agent is as follows.
A, by each component by above-mentioned ratio of weight and number dispensing, difference is successively in metered mixer；
B, mixture by deep processing is ground into powder material, is sufficiently mixed under batch mixer, obtains desulfurizing agent dry powder；
C, aqua is blent by the reducing agent of certain mass and the water of certain mass, is sufficiently mixed the homogeneous that stirs to get Water-soluble reducing agent.
3rd, the specifically used method of cement kiln catalytic desulfurizing agent.
A, enter setting desulphurization denitration complexing agent bulk pot by kiln elevator, pass through the electron helical scale tune under bulk pot Speed metering, is equably added into mash form in kiln elevator；Aqua adjusts flow by fluid flowmeter, is pumped through conveying To preheater C2 uptake flues, equipped with atomizer in flue, to ensure the atomizing effect of aqua.B, desulfurization powder addition The 0.10%~1.50% of raw material weight is accounted for, aqua dosage is 1.0~3.0m3/h；Depending on sulfide emission amount and raw material Feeding capacity gives.
4th, using effect.When new type dry kiln with desulphurization denitration complexing agent mix that weight ratio is raw meal quality outside 0.10%~ 1.50%, it, generally can emission reduction SO2 >=90%, SO2 discharge capacity≤100mg/m when aqua dosage is 1.0~3.0m3/h3。
The above-mentioned example of the present invention is only example to illustrate the invention, and is not the limit of embodiments of the present invention It is fixed.Other different forms of changes or modifications may be made based on the above description, does not enumerate herein.It is every Belong to obvious changes or variations that technical scheme is extended out still in protection scope of the present invention.

Claims (5)

1. a kind of new dry process rotary kiln catalytic desulfurizing agent, includes pulvis and aqua two parts, it is characterised in that：Wherein, pulvis The mass percent of each component is calcium carbonate：45~65%, calcium oxide:28~45%, iron oxide:0.1~1%, magnesia: 1~6.5%, barium carbonate:0.5~1.5%, rare element compound:1~5%, silica:3-5.5%, surplus are white Marble, the sum of fluorite, each component are 100%；
It is as follows that rare element compound each component accounts for total rare element total amount of compound mass percent：Manganese dioxide 70~ 80%th, titanium dioxide 15~20%, ceria 2~6%, 0 .5~5% of lithium hydroxide, oxidant：The sum of 1-3%, each component For 100%；
Pulvis additive amount is the 0.1~1.5% of cement raw meal quality, and aqua is the reducing agent for being dissolved in water, and aqua dosage is 1.0 ~3.0m3/h.
2. new dry process rotary kiln catalytic desulfurizing agent according to claim 1, it is characterized in that：The oxidizer composition is carbonic acid Hydrogen ammonia and nitric acid ammonia.
3. new dry process rotary kiln catalytic desulfurizing agent according to claim 1, it is characterized in that：The reducing agent ingredient is NH3, Concentration is 3-6w%.
4. a kind of new dry process rotary kiln catalytic desulfurizing agent preparation method described in claim 1, it is characterised in that：Preparation method walks It is rapid as follows,
A, by each component by above-mentioned weight ratio dispensing, difference is successively in metered mixer；
B, mixture by deep processing is ground into powder material, is sufficiently mixed under batch mixer, obtains desulfurizing agent dry powder；
C, reducing agent and water are blent in proportion, is sufficiently mixed the water-soluble reducing agent for stirring to get homogeneous.
5. a kind of new dry process rotary kiln catalytic desulfurizing agent application method described in claim 1, it is characterised in that：A, carry entering kiln Desulphurization denitration complexing agent bulk pot by the machine of liter is set, is measured by the electron helical scale speed governing under bulk pot, with mash form Uniformly it is added into kiln elevator；Aqua adjusts flow by fluid flowmeter, and preheater C2 uptake flues are pumped to through conveying It is interior, it is sprayed through the atomization nozzle of flue, to ensure the atomizing effect of aqua；
B, desulfurization powder addition accounts for the 0.10%~1.50% of raw material weight, and aqua dosage is 1.0~3.0m3/h, depending on Sulfide emission amount and raw material feeding capacity give.
CN201711190438.0A 2017-11-24 2017-11-24 A kind of new dry process rotary kiln catalytic desulfurizing agent and its preparation and application Pending CN108079776A (en)

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108793789A (en) * 2018-06-25 2018-11-13 南京永能新材料有限公司 A kind of desulfurizing agent and preparation method thereof in cement production process
CN110508115A (en) * 2019-09-09 2019-11-29 昆明理工大学 A kind of desulfurizing agent and preparation method and application
CN110550876A (en) * 2019-10-08 2019-12-10 安徽宇睿环保科技有限公司 Sulfur dioxide desulfurization method
CN110981239A (en) * 2019-12-26 2020-04-10 中海油天津化工研究设计院有限公司 Combined desulfurization and denitrification method for novel dry-process cement production line
CN111111773A (en) * 2019-12-26 2020-05-08 辽宁鑫隆科技有限公司 Desulfurization and denitrification catalyst for cement production
CN111359653A (en) * 2020-04-07 2020-07-03 中海油天津化工研究设计院有限公司 Catalyst for improving desulfurization performance of calcium oxide
CN112742188A (en) * 2020-12-11 2021-05-04 马鞍山市国林建材有限公司 Preparation method of efficient dry cement desulfurizer for producing Z-shaped concrete hollow blocks
CN113083340A (en) * 2021-04-09 2021-07-09 河南汇金智能装备有限公司 Catalyst for inhibiting decomposition of calcium sulfate, high-efficiency catalytic desulfurization powder containing catalyst and application method of high-efficiency catalytic desulfurization powder
CN114011235A (en) * 2020-12-15 2022-02-08 广州泰科节能环保科技有限公司 Flue gas catalytic desulfurizer, preparation method and application thereof

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108793789A (en) * 2018-06-25 2018-11-13 南京永能新材料有限公司 A kind of desulfurizing agent and preparation method thereof in cement production process
CN110508115A (en) * 2019-09-09 2019-11-29 昆明理工大学 A kind of desulfurizing agent and preparation method and application
CN110508115B (en) * 2019-09-09 2021-07-27 昆明理工大学 Desulfurizing agent, preparation method and application
CN110550876A (en) * 2019-10-08 2019-12-10 安徽宇睿环保科技有限公司 Sulfur dioxide desulfurization method
CN110550876B (en) * 2019-10-08 2021-09-17 安徽宇睿环保科技有限公司 Sulfur dioxide desulfurization method
CN110981239A (en) * 2019-12-26 2020-04-10 中海油天津化工研究设计院有限公司 Combined desulfurization and denitrification method for novel dry-process cement production line
CN111111773A (en) * 2019-12-26 2020-05-08 辽宁鑫隆科技有限公司 Desulfurization and denitrification catalyst for cement production
CN111359653A (en) * 2020-04-07 2020-07-03 中海油天津化工研究设计院有限公司 Catalyst for improving desulfurization performance of calcium oxide
CN112742188A (en) * 2020-12-11 2021-05-04 马鞍山市国林建材有限公司 Preparation method of efficient dry cement desulfurizer for producing Z-shaped concrete hollow blocks
CN114011235A (en) * 2020-12-15 2022-02-08 广州泰科节能环保科技有限公司 Flue gas catalytic desulfurizer, preparation method and application thereof
CN113083340A (en) * 2021-04-09 2021-07-09 河南汇金智能装备有限公司 Catalyst for inhibiting decomposition of calcium sulfate, high-efficiency catalytic desulfurization powder containing catalyst and application method of high-efficiency catalytic desulfurization powder
CN113083340B (en) * 2021-04-09 2023-11-14 河南汇金智能装备有限公司 Catalyst for inhibiting calcium sulfate decomposition, high-efficiency catalytic desulfurization powder containing catalyst and application method

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