CN110981239A - Combined desulfurization and denitrification method for novel dry-process cement production line - Google Patents

Combined desulfurization and denitrification method for novel dry-process cement production line Download PDF

Info

Publication number
CN110981239A
CN110981239A CN201911365007.2A CN201911365007A CN110981239A CN 110981239 A CN110981239 A CN 110981239A CN 201911365007 A CN201911365007 A CN 201911365007A CN 110981239 A CN110981239 A CN 110981239A
Authority
CN
China
Prior art keywords
denitrification
desulfurization
raw material
clay
production line
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201911365007.2A
Other languages
Chinese (zh)
Inventor
苏少龙
曲晓龙
钟读乐
孙彦民
南军
李世鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
Original Assignee
CNOOC Energy Technology and Services Ltd
CNOOC Tianjin Chemical Research and Design Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CNOOC Energy Technology and Services Ltd, CNOOC Tianjin Chemical Research and Design Institute Co Ltd filed Critical CNOOC Energy Technology and Services Ltd
Priority to CN201911365007.2A priority Critical patent/CN110981239A/en
Publication of CN110981239A publication Critical patent/CN110981239A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • B01D53/60—Simultaneously removing sulfur oxides and nitrogen oxides
    • 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
    • B01D53/75—Multi-step 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • 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
    • 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
    • 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
    • B01D2258/0233—Other waste gases from cement factories
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Biomedical Technology (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention discloses a combined desulfurization and denitrification method for a novel dry-process cement production line. The method comprises the steps of adding a raw material modifier and a liquid desulfurization and denitrification agent into a cement production line, wherein the raw material modifier is added at a raw material hoister, and the liquid desulfurization and denitrification agent is added at an upper air pipe between C1 and C3 of a cyclone preheater; the raw material modifier comprises 10-98% of SO2Absorbent, 0.01-30% of promoted SO2The denitration catalyst comprises the components of 0.01-30% of an absorbed active component, 0.01-30% of an active component for promoting the decomposition of limestone and 0.01-30% of a clay as a carrier; the liquid desulfurization and denitrification agent comprises 0.1-25% of ammonia water, 0.1-40% of urea solution or mixed solution of the two. The invention has the technical advantages of good desulfurization and denitrification effects, low cost and no secondary pollution.

Description

Combined desulfurization and denitrification method for novel dry-process cement production line
The technical field is as follows:
the invention relates to a combined desulfurization and denitrification method for a novel dry-process cement production line.
Background art:
with the increasing emphasis on environmental problems in China, the pollutant discharge of enterprises is strictly limited. Sulfur dioxide and nitrogen oxides are important indexes for controlling emission in the cement industry in China. Sulfur dioxide has an irritating odor and can cause acid rain; nitrogen oxides can cause problems such as photochemical smog, acid rain, ozone layer destruction, and the like. The two cause serious harm to the ecological environment, and cause high concern of the country.
The commonly used desulfurization techniques include dry desulfurization, semi-dry desulfurization and wet desulfurization. The dry desulfurization has the disadvantages of low desulfurization efficiency; the disadvantage of wet desulphurization is that the equipment investment is huge; the semi-dry desulfurization solves the defects of dry desulfurization and wet desulfurization to a certain extent, but the occupied space of the equipment is larger. The cement industry denitration technology mainly comprises an SCR denitration technology, an SNCR denitration technology, an LCO method flue gas purification integrated large-scale oxygen-reducing machine denitration technology and an AC-GTsx flue gas desulfurization and denitration technology. Among them, the SNCR denitration technology is applied more. However, the SNCR denitration technique has a disadvantage of low denitration efficiency. At present, aiming at a novel dry-method cement production line, a desulfurization and denitrification technology with good effect, low cost and no secondary pollution is provided.
The invention content is as follows:
aiming at the defects of the desulfurization and denitrification technology of the existing novel dry-method cement production line, the invention provides a combined desulfurization and denitrification method aiming at the novel dry-method cement production line.
The invention solves the technical problems and adopts the following technical means:
a combined desulfurization and denitrification method for a novel dry-process cement production line comprises the steps of adding a raw material modifier and a liquid desulfurization and denitrification agent into the cement production line, wherein the raw material modifier is added at a raw material lifter, and the liquid desulfurization and denitrification agent is added at an air inlet pipe between a cyclone preheater C1-C3;
the raw material modifier comprises 10-98% wtSO20.01-30 wt% of SO as an absorbent2The denitration catalyst comprises the components of 0.01-30 wt% of an absorbed active component, 0.01-30 wt% of an active component for promoting the decomposition of limestone and 0.01-30 wt% of a denitration catalyst taking clay as a carrier;
the liquid desulfurization and denitrification agent comprises 0.1-25 wt% of ammonia water, 0.1-40 wt% of urea solution or a mixed solution of the two.
The combined desulfurization and denitrification method of the invention is characterized in that the SO2The absorbent comprises one or more of calcium hydroxide, calcium oxide, calcium carbonate and zinc oxide.
Said promoting SO2The absorbed active components comprise one or more of rare earth oxides and ferric oxide.
The active component for promoting the decomposition of the limestone is selected from organic acid and metal oxide, and the organic acid is citric acid, oxalic acid and tartaric acid; the metal oxide is CuO or Cr2O3、PbO、ZnO、Al2O3、ZrO2、B2O3。
The denitration catalyst taking clay as a carrier is clay loaded with iron, copper, manganese, titanium, tungsten or rare earth elements. The clay in the denitration catalyst taking the clay as the carrier is one or more of kaolinite, turpentine, montmorillonite, vermiculite, illite and allophane.
Compared with the prior art, the combined desulfurization and denitrification method for the novel dry-process cement production line has the following advantages:
(1) according to the invention, desulfurization and denitrification can be realized in the production process without adding rear-end desulfurization and denitrification equipment, so that the cost is effectively reduced;
(2) the method couples the desulfurization and denitrification processes with the cement production process, and the desulfurization and denitrification products are converted into cement clinker, so that the capacity of the cement clinker is increased, and no secondary pollution is generated;
(3) and the near zero emission of sulfur dioxide and nitrogen oxide can be realized by matching with a rear-end desulfurization and denitrification technology.
Therefore, the method has the technical advantages of good desulfurization and denitrification effects, low cost and no secondary pollution.
The specific implementation mode is as follows:
the technical solution of the present invention is further illustrated by the following specific examples.
[ example 1 ]
Dissolving 20kg of ferric nitrate and 20kg of copper nitrate in 200kg of water, adding 100kg of commercially available kaolinite, soaking for 2h, and filtering to obtain filter residue. And drying the filter residue at 100 ℃ for 5h, and roasting at 500 ℃ for 5h to obtain the denitration catalyst taking clay as a carrier. 5000kg of calcium hydroxide is added with 50kg of ferric oxide and 50kg of copper oxide, and 100kg of denitration catalyst taking clay as a carrier to obtain the raw material modifier. And taking 12% ammonia water solution as a liquid desulfurization and denitrification agent. For a novel dry-process cement production line producing 2500 tons of clinker per day, the emission concentration of the sulfur dioxide at the background is 400mg/m3The nitrogen oxide emission concentration is 400mg/m3. Raw material modifier is added through a raw material warehouse elevator, the adding amount is 5000kg/h, liquid desulfurization and denitrification agent is added through a spray gun to an upper air pipe of a cyclone preheater C1-C2, and the adding amount is 3000 kg/h. After 30min, the concentration of sulfur dioxide and nitrogen oxide reaches the equilibrium state, wherein the emission concentration of sulfur dioxide is lower than 35mg/m3The emission concentration of nitrogen oxides is lower than 50mg/m3。
[ example 2 ]
Dissolving 20kg of ferric nitrate and 20kg of cerous nitrate in 200kg of water, adding 100kg of commercially available kaolinite, soaking for 2h, and filtering to obtain filter residue. And drying the filter residue at 100 ℃ for 5h, and roasting at 500 ℃ for 5h to obtain the denitration catalyst taking clay as a carrier. 5000kg of calcium hydroxide is added with 80kg of ferric oxide, 80kg of copper oxide and 100kg of denitration catalyst taking clay as a carrier to obtain the raw material modifier. And taking 12% ammonia water solution as a liquid desulfurization and denitrification agent. For a novel dry-process cement production line producing 2500 tons of clinker per day, the emission concentration of the sulfur dioxide at the background is 400mg/m3The nitrogen oxide emission concentration is 400mg/m3. Raw material modifier is added through a raw material warehouse elevator, the adding amount is 5000kg/h, and liquid desulfurization and denitrification agent is added to the upper air pipe of a cyclone preheater C1-C2 through a spray gunThe addition was 3000 kg/h. After 30min, the concentration of sulfur dioxide and nitrogen oxide reaches the equilibrium state, wherein the emission concentration of sulfur dioxide is lower than 35mg/m3The emission concentration of nitrogen oxides is lower than 50mg/m3。
[ example 3 ]
Dissolving 15kg of ferric nitrate and 15kg of cerous nitrate in 200kg of water, adding 100kg of commercially available kaolinite, soaking for 2h, and filtering to obtain filter residue. And drying the filter residue at 100 ℃ for 5h, and roasting at 500 ℃ for 5h to obtain the denitration catalyst taking clay as a carrier. 100kg of ferric oxide and 100kg of copper oxide are added into 5000kg of calcium hydroxide, and 100kg of denitration catalyst taking clay as a carrier is added to obtain the raw material modifier. And taking 12% ammonia water solution as a liquid desulfurization and denitrification agent. For a novel dry-process cement production line producing 2500 tons of clinker per day, the emission concentration of the sulfur dioxide at the background is 400mg/m3The nitrogen oxide emission concentration is 400mg/m3. Raw material modifier is added through a raw material warehouse elevator, the adding amount is 5000kg/h, liquid desulfurization and denitrification agent is added through a spray gun to an upper air pipe of a cyclone preheater C1-C2, and the adding amount is 3000 kg/h. After 30min, the concentration of sulfur dioxide and nitrogen oxide reaches the equilibrium state, wherein the emission concentration of sulfur dioxide is lower than 35mg/m3The emission concentration of nitrogen oxides is lower than 50mg/m3。

Claims (7)

1. A combined desulfurization and denitrification method for a novel dry-process cement production line is characterized by comprising the steps of adding a raw material modifier and a liquid desulfurization and denitrification agent into the cement production line, wherein the raw material modifier is added at a raw material lifter, and the liquid desulfurization and denitrification agent is added at an air inlet pipe between a cyclone preheater C1 and a cyclone preheater C3;
the raw material modifier comprises 10-98 wt% of SO20.01-30 wt% of SO as an absorbent2The denitration catalyst comprises the components of 0.01-30 wt% of an absorbed active component, 0.01-30 wt% of an active component for promoting the decomposition of limestone and 0.01-30 wt% of a denitration catalyst taking clay as a carrier;
the liquid desulfurization and denitrification agent comprises 0.1-25 wt% of ammonia water, 0.1-40 wt% of urea solution or a mixed solution of the two.
2. The integrated desulfurization and denitrification process of claim 1, wherein the SO is2The absorbent comprises one or more of calcium hydroxide, calcium oxide, calcium carbonate and zinc oxide.
3. The integrated desulfurization and denitrification process of claim 1, wherein the SO-promoted product is2The absorbed active components comprise one or more of rare earth oxides and ferric oxide.
4. The integrated desulfurization and denitrification method according to claim 1, wherein the active component for promoting the decomposition of limestone is selected from the group consisting of organic acids and metal oxides.
5. The integrated desulfurization and denitrification method according to claim 4, wherein the organic acid is citric acid, oxalic acid, tartaric acid; the metal oxide is CuO or Cr2O3、PbO、ZnO、Al2O3、ZrO2、B2O3。
6. The integrated desulfurization and denitrification method according to claim 1, wherein the clay-supported denitrification catalyst is clay loaded with iron, copper, manganese, titanium, tungsten or rare earth elements.
7. The integrated desulfurization and denitrification method according to claim 1, wherein the clay in the clay-supported denitrification catalyst is one or more of kaolinite, petrolatum, montmorillonite, vermiculite, illite and allophane.
CN201911365007.2A 2019-12-26 2019-12-26 Combined desulfurization and denitrification method for novel dry-process cement production line Pending CN110981239A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911365007.2A CN110981239A (en) 2019-12-26 2019-12-26 Combined desulfurization and denitrification method for novel dry-process cement production line

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911365007.2A CN110981239A (en) 2019-12-26 2019-12-26 Combined desulfurization and denitrification method for novel dry-process cement production line

Publications (1)

Publication Number Publication Date
CN110981239A true CN110981239A (en) 2020-04-10

Family

ID=70077096

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911365007.2A Pending CN110981239A (en) 2019-12-26 2019-12-26 Combined desulfurization and denitrification method for novel dry-process cement production line

Country Status (1)

Country Link
CN (1) CN110981239A (en)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0530898A1 (en) * 1991-09-03 1993-03-10 STEAG Aktiengesellschaft Method for operating a coal-fired power plant
CN106732751A (en) * 2016-12-08 2017-05-31 盐城工学院 A kind of desulphurization denitration catalyst and preparation method thereof and application method
CN108079776A (en) * 2017-11-24 2018-05-29 北京绿岩环保科技有限责任公司 A kind of new dry process rotary kiln catalytic desulfurizing agent and its preparation and application

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0530898A1 (en) * 1991-09-03 1993-03-10 STEAG Aktiengesellschaft Method for operating a coal-fired power plant
CN106732751A (en) * 2016-12-08 2017-05-31 盐城工学院 A kind of desulphurization denitration catalyst and preparation method thereof and application method
CN108079776A (en) * 2017-11-24 2018-05-29 北京绿岩环保科技有限责任公司 A kind of new dry process rotary kiln catalytic desulfurizing agent and its preparation and application

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
吴晓东等: "《稀土催化材料》", 30 June 2017, 中国铁道出版社 *
张蕾等: "《烟气脱硫脱硝技术及催化剂的研究进展》", 31 August 2016, 中国矿业大学出版社 *
贡俊等: "《微生物法脱除二氧化硫气体的研究》", 31 December 2011, 中国环境科学出版社 *

Similar Documents

Publication Publication Date Title
CN106179326B (en) A kind of nano tube supported type denitrating catalyst of manganese oxide and preparation method thereof
CN101249373B (en) Flue gas desulfurization agent preparation method
CN106732751B (en) Desulfurization and denitrification catalyst, and preparation method and use method thereof
CN1792455A (en) Cellular activated-carbon catalyst used for denitrification of flue-gas, prepn. method and application thereof
US11339091B2 (en) Cementitious material and production method thereof
CN111545040B (en) Composite denitration agent and preparation method thereof
CN110404936B (en) Comprehensive treatment method for semi-dry desulfurized fly ash
CN101632897B (en) Method for simultaneously removing sulfur oxides and nitric oxides in flue gas
CN102701618A (en) Method for using calcium sulfite type desulfurization gypsum to produce high-strength environmental-friendly type plastering gypsum
CN100528345C (en) Denitration catalyst, and preparation method
CN110893312A (en) Novel high-efficiency desulfurizer and preparation method thereof
CN102794097A (en) Flue gas wet-type reduction integrated desulfurization and denitration and harmless processing and resource utilization method
CN111545049A (en) SNCR (Selective non catalytic reduction) denitration system and method for removing escaping ammonia in SNCR denitration process
CN107626292A (en) Flue gas desulfurization and denitrification catalyst and its preparation method and application
CN102824836A (en) Integrated wet-type oxidation, desulfurization, denitration and recycling method for smoke
CN106178862A (en) Sintering smoke denitrifier and preparation method thereof
CN1736559A (en) Ammonia-ammonia sulfate dry type flue gas desulfurizing denitrifying equipment and technique
CN107812441A (en) Flue gas dry desulfurizing method of denitration based on red mud
CN107866142B (en) A processing system that is used for cement trade dry process SOx/NOx control accessory substance
CN114011400A (en) Preparation method of acid system waste incineration SCR denitration catalyst and prepared denitration catalyst
CN110981239A (en) Combined desulfurization and denitrification method for novel dry-process cement production line
CN109621713B (en) Sludge composite denitration agent and preparation and application thereof
CN109174097B (en) Catalyst for desulfurization and denitrification of metallurgical sintering flue gas and preparation method thereof
CN207405091U (en) For the disposal system of cement industry dry desulfurization denitration by-product
CN110787617B (en) Sintering flue gas semi-dry desulfurization and denitrification integrated device and method

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20200410

RJ01 Rejection of invention patent application after publication