CN107903921A - A kind of carbon emission reduction system for coupling manufacture of cement and spent bleaching clay and recycling - Google Patents

A kind of carbon emission reduction system for coupling manufacture of cement and spent bleaching clay and recycling Download PDF

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Publication number
CN107903921A
CN107903921A CN201711083562.7A CN201711083562A CN107903921A CN 107903921 A CN107903921 A CN 107903921A CN 201711083562 A CN201711083562 A CN 201711083562A CN 107903921 A CN107903921 A CN 107903921A
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cement
spent bleaching
bleaching clay
calcining furnace
outlet
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CN107903921B (en
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段伦博
苏成林
陈健
崔健
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Southeast University
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Southeast University
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • 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
    • B01D53/62—Carbon 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
    • B01D53/81—Solid phase processes
    • 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
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
    • 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

Abstract

The present invention disclose a kind of carbon emission reduction system for coupling manufacture of cement and spent bleaching clay and recycling, which mainly includes being carbonated the devices such as stove (1), calcining furnace (2), spent bleaching clay pyrolysis oven (3), granulator (4), kiln (5), cooler (6), flour mill (7), cyclone separator (8 1) and (8 2), heat exchanger (9 1) and (9 2)；Wherein based on be carbonated stove and calcining furnace, the carbon trapping system of composition is used to catch the CO in flue gas2；The pyrolysis gas produced by spent bleaching clay pyrolysis oven enters calcining furnace, there is provided the hot conditions needed for calcium-base absorbing agent regeneration, reduce the cost input of carbon trapping system；The shaping calcium-base absorbing agent that clay dregs blended cement and lime burning stone powder after pyrolysis prepare high activity enters calcining furnace；The inactivation calcium-base absorbing agent of calcining furnace discharge is used as the raw material of manufacture of cement, further reduces the CO in cement plant2Discharge capacity.

Description

A kind of carbon emission reduction system for coupling manufacture of cement and spent bleaching clay and recycling
Technical field
The present invention relates to spent bleaching clay recycling, manufacture of cement and calcium circularly trapping CO2The combination of technology, belongs to water Mud produces and environmental protection technology crossing domain.
Background technology
In November, 2016, it is intended to control greenhouse effects《Reach an agreement in Paris》Formally effective, China is real before promising to undertake the year two thousand thirty Existing CO2Particle emission peak, and will strive to realize this target in advance, except coal fired power plant, manufacture of cement is main CO2Emission source One of, not only due to the high energy consumption of cement production process, the process that calcined limestone prepares clinker also exceedes contribution 50% CO2Discharge capacity.China is manufacture of cement big country, and Chinese cement output is 24.78 hundred million tons within 2014, occupies the whole world The 59% of cement total output, contribute to 15% share of total carbon emission.
Post-combustion capture CO2Technology is that have one of carbon emission reduction technology of development prospect, wherein in calcium round-robin method technique, is made With cheap, the natural calcium-base absorbing agent (such as lime stone, dolomite) of rich reserves, possesses certain economy.Calcium follows Loop system mainly includes calcination reactor and carbonation reactor, calcium-base absorbing agent (temperature in calcination reactor>900 DEG C) hair Raw calcination reaction, generates high concentration CO2And CaO；High concentration CO2Stream subsequently exchange heat, compress and store, and CaO then enters carbonic acid Change the CO in reactor (temperature~650 DEG C) trapping flue gas2, generate CaCO3.And so on, absorbent is circulated in systems Reaction.The influence factor of calcium circulatory system economy is mainly comprising two aspects：First, maintaining the high temperature level in calcining furnace, need Extra fuel is provided；Second, the heat endurance of natural calcium-base absorbing agent is poor, since sintering causes to absorb in circular response Performance sharp-decay is, it is necessary to persistently supplement fresh absorbent to maintain required trapping ability, increase Material Cost.System is discharged Inactivation absorbent can be as the raw material of manufacture of cement, so as to improve the economy of system entirety.By using solid waste Thing prepares or modified calcium-base absorbent, can effectively improve the economy of the calcium circulatory system.But based on cement standard component It is required that requirement is proposed to the component of calcium-base absorbing agent modified material, to meet follow-up manufacture of cement needs.
Due to being widely used in edible oil and refined course of lubricating oil with higher active surface area, atlapulgite.Essence The spent bleaching clay of process discharge processed, oil content are up to 30%.According to statistics, the total output point of 2015 annual China's edible oils and lubricating oil Wei not be 2743. and 3,720,000 tons, calculated with the atlapulgite dosage of 1~6wt.%, at least generate 300,000 tons of spent bleaching clays.Landfill It is the major way of current disposal spent bleaching clay, not only causes environmental pollution, but also waste the crude oil of absorption.That studies at present is useless Clay regeneration method, it is main to include heat treatment, acid solution processing, supercritical CO2Extraction and organic solvent extraction, wherein to have The rate of recovery highest of solvent extraction, carclazyte activation recovering degree highest, but complex operation, it is of high cost, reduce The economy of technique.
The content of the invention
Technical problem：In order to further improve the economy of calcium looping process, the new way of spent bleaching clay recycling is explored Footpath, the present invention provides a kind of efficient carbon trapping system for coupling manufacture of cement and spent bleaching clay and recycling, by regenerated clay powder recycling Fuel, partly or entirely substitute the high value fuel in calcium looping process used in calcination reactor, the carclazyte after regeneration Slag and cement are used for modified calcium-base absorbent, improve the anti-caking power of absorbent, reduce the consumption of fresh absorbent, modified Calcium-base absorbing agent meet the component requirements of manufacture of cement, therefore the absorbent inactivated can be used as raw material to be used for cement life Production, reduces because of the CO of calcined limestone discharge2Amount.
The content of the invention：Recycled in order to solve the above technical problems, the present invention provides a kind of coupling manufacture of cement and spent bleaching clay Carbon emission reduction system, the system mainly include carbonating stove, calcining furnace, spent bleaching clay pyrolysis oven, granulator, kiln, cooling Machine, flour mill, the first cyclone separator, the second cyclone separator, First Heat Exchanger, First Heat Exchanger；Wherein,
The pyrolysis gas outlet on spent bleaching clay pyrolysis oven top is connected with the fuel inlet of calcining furnace, the bottom ash of spent bleaching clay pyrolysis oven The outlet of the finished ground cement of outlet and cement plant flour mill is connected with the material inlet of granulator, the shaped granule outlet of granulator It is connected with the absorbent entrance of calcining furnace；
The outlet of inactivation absorbent is connected with the material inlet of rotary cement kiln stove in calcining furnace；The thing of kiln Material outlet is connected with cooler entrance, and cooler outlet is connected with the entrance of flour mill；
The exhanst gas outlet of kiln is connected with carbonating furnace bottom fluidized wind entrance；Be carbonated stove and the first cyclonic separation The CaCO of device3Outlet and the CaCO of calcining furnace3Entrance is connected；Equally, the CaO of calcining furnace and the second cyclone separator outlets and carbon Acidifying stove CaO entrances are connected；The exhanst gas outlet of first cyclone separator and the second cyclone separator respectively with First Heat Exchanger and The smoke inlet of second heat exchanger is connected.
The carbonating stove is fluidized-bed reactor.
The calcining furnace is fluidized-bed reactor.
The operating temperature range of the spent bleaching clay pyrolysis oven is 500 DEG C~800 DEG C, and pyrolysis oven institute's calorific requirement is by partly following The sensible heat that ring pyrolysis gas carries provides, and pyrolysis gas internal circulating load is 10%~20%.
The absorbent, mass component 85%CaCO3, 5% pyrolysis clay dregs, 10% cement.
The granulator is high speed wet granulator, and making binding agent with deionized water in pelletization is granulated the day that uses Right calcium-base absorbing agent is lime stone or dolomite, is pyrolyzed clay dregs and cement additive amount and is all no more than 20%.
Beneficial effect：
1. the new way of a spent bleaching clay recycling is explored, by the recycling of spent bleaching clay and calcium circularly trapping CO2 Technology is combined, and improves the use value of spent bleaching clay；
2. with the fuel of regenerated clay powder recycling, the high value combustion consumed in the calcium circulatory system in calcination reactor is substituted Material, can reduce fuel cost；The calcium-base absorbing agent of spent bleaching clay and modified cement is regenerated, anti-caking power improves, and reduces fresh The consumption of absorbent, so as to reduce absorbent cost；
3. by the calcium-base absorbing agent of inactivation be used as manufacture of cement raw material, can effectively reduce because calcined limestone prepare it is ripe The CO of material2Discharge capacity.
Brief description of the drawings
Fig. 1 is apparatus of the present invention schematic diagram.
Included in figure：Be carbonated stove 1, calcining furnace 2, spent bleaching clay pyrolysis oven 3, granulator 4, kiln 5, cooler 6, mill Powder machine 7, the first cyclone separator 8-1, the second cyclone separator 8-2, First Heat Exchanger 9-1, the second heat exchanger 9-2.
Embodiment
The present invention is done with reference to embodiment and attached drawing and is further explained.Following embodiments do not limit in any form The system present invention, all technical solutions obtained by the way of equivalent substitution or equivalent transformation, are in protection model of the invention Among enclosing.
In the present invention, by spent bleaching clay regeneration techniques, cement production process and calcium round-robin method trapping CO2Technique is combined, energy Enough realize that the high value of spent bleaching clay utilizes, improve the economy of system entirety.The combustion of renovation process recycling is pyrolyzed by spent bleaching clay Material (pyrolysis gas) enters calcining furnace, instead of high value fuel, maintains calcining furnace high temperature；Clay dregs after regeneration include a certain amount of Indifferent oxide and carbon residue are mixed with cement and lime burning stone powder, prepare the shaping calcium-base absorbing agent of high activity, are entered Calcining furnace participates in Cyclic Calcination carbonation reaction；The inactivation modified calcium-base absorbent of calcium circulatory system discharge, due to meeting cement The component requirements of production, are suitable as raw material and are used to produce clinker, therefore can reduce dinectly bruning lime stone and prepare CaO Share so that reduce conventional cement production CO2Discharge capacity, the cement that final production goes out, a part are used to prepare high activity Absorbent granules, so as to fulfill the coupling of cement production process and calcium looping process.
The pyrolysis gas outlet of spent bleaching clay pyrolysis oven 3 is connected with the fuel inlet of calcining furnace 2, the bottom ash of spent bleaching clay pyrolysis oven 3 The outlet of the finished ground cement of outlet and cement plant flour mill 7 is connected with the material inlet of granulator 4, the shaped granule of granulator 4 Outlet is connected with the absorbent entrance of calcining furnace 2；The operating temperature range of the spent bleaching clay pyrolysis oven is；Spent bleaching clay regeneration side Method includes heat treating process, method of chemical treatment, supercritical CO2Extraction and organic solvent extractionprocess etc.；Tieed up in the calcining furnace The energy needed for high temperature is held, the high-temperature flue gas sensible heat produced by the oil, pyrolysis gas and calcining that are produced from spent bleaching clay regeneration There is provided Deng energy；The granulator can be the machines such as fluidized bed spray granulation machine, high speed wet granulator and extrusion forming Tool, it is lime stone or dolomite etc. to be granulated the natural calcium-base absorbing agent used.
The outlet of inactivation absorbent is connected with the material inlet of rotary cement kiln stove 5 in calcining furnace 2；Kiln 5 Material outlet be connected with 6 entrance of cooler, cooler 6 outlet is connected with the entrance of flour mill 7；
The exhanst gas outlet of boiler and kiln 5 is connected with carbonating 1 bottom fluidization wind entrance of stove；Be carbonated stove 1 and the The CaCO of one cyclone separator 8-13Outlet and the CaCO of calcining furnace 23Entrance is connected；Equally, 2 and second cyclonic separation of calcining furnace The CaO outlets of device 8-2 are connected with the CaO entrances for the stove 1 that is carbonated；First cyclone separator 8-1's and the second cyclone separator 8-2 Smoke inlet of the exhanst gas outlet respectively with First Heat Exchanger 9-1 and the second heat exchanger 9-2 is connected.
For the system proposed in the present invention, the rough calculation of heat balance and material balance is carried out, is refined with sinopec The spent bleaching clay of oily factory is sample, and it is 30% to measure the oil content of spent bleaching clay to take oil content at 25%~35%, calculating through experiment, The calorific value 10000kcal/kg of fuel oil, the combustion heat that can be calculated 1kg spent bleaching clays recycling oil is 10000*4.18585*0.3 =12557.6kJ, the combustion heat that gained is calculated with contained oil in spent bleaching clay replace combustion heat release of the pyrolysis gas in calcining furnace Amount, it is assumed that enter the CaCO of calcining furnace from carbonating stove3Temperature is 650 DEG C, Isothermal Structural Decomposition In Certain after being heated to 900 DEG C, CaCO3 Shown in the thermochemical equation of high-temperature decomposition reaction such as formula (1), reaction heat is obtained, calculation equation by Kiel dagger-axe husband equation calculation As shown in formula (2),
Can be calculated Δ H is 209.6kJ/mol, that is, calcines 1kg CaCO3Required energy is 2096kJ, with composite absorber Material composition is 80%CaCO3Exemplified by/10% pyrolysis cement of clay dregs/10%, carried out with 50% average carbonate treatment rate Calculate, calcine energy Q needed for 1kg composite absorber particles1=2096*0.8*0.5=838.4kJ；Corresponding spent bleaching clay produces heat Vent one's spleen the energy Q that can be provided2=12557.6*0.1/0.7=1793.9kJ.Due to Q2>Q1, under the conditions of assumed above, pyrolysis Clay dregs are completely used for preparing absorbent, and absorbent can be provided completely twice needed for calcining and decomposing with caused pyrolysis gas Energy.When carrying out multi-cycle reaction, it is necessary to which consuming additional fuel provides required calcining heat.
Absorbent traps performance experimental result and shows, component 85%CaCO3/ 5% pyrolysis cement of clay dregs/10% is answered It is best to close the trapping performance of absorbent granules, is calculated with 50% average carbonate treatment rate, 1kg composite absorber particles Required energy Q1'=2096*0.85*0.5=890.5kJ；Corresponding spent bleaching clay produces the energy Q that pyrolysis gas can be provided2'= 12557.6*0.05/0.7=897.0kJ.Due to Q2’>Q1', under the conditions of assumed above, pyrolysis clay dregs, which are completely used for preparing, to be inhaled Agent is received, the energy needed for absorbent single calcining and decomposing can be provided completely with caused pyrolysis gas.When carrying out, multi-cycle is anti- At once, it is necessary to which consuming additional fuel provides required calcining heat.

Claims (6)

1. a kind of carbon emission reduction system for coupling manufacture of cement and spent bleaching clay and recycling, it is characterised in that the system mainly includes carbon It is acidified stove (1), calcining furnace (2), spent bleaching clay pyrolysis oven (3), granulator (4), kiln (5), cooler (6), flour mill (7), the first cyclone separator (8-1), the second cyclone separator (8-2), First Heat Exchanger (9-1), First Heat Exchanger (9-2)； Wherein,
The pyrolysis gas outlet on spent bleaching clay pyrolysis oven (3) top is connected with the fuel inlet of calcining furnace (2), spent bleaching clay pyrolysis oven (3) Bottom ash outlet and cement plant flour mill (7) finished ground cement outlet be connected with the material inlet of granulator (4), granulator (4) shaped granule outlet is connected with the absorbent entrance of calcining furnace (2)；
The outlet of inactivation absorbent is connected with the material inlet of rotary cement kiln stove (5) in calcining furnace (2)；Kiln (5) material outlet is connected with cooler (6) entrance, and cooler (6) outlet is connected with the entrance of flour mill (7)；
The exhanst gas outlet of kiln (5) is connected with carbonating stove (1) bottom fluidization wind entrance；Be carbonated stove (1) and the first rotation The CaCO of wind separator (8-1)3Outlet and the CaCO of calcining furnace (2)3Entrance is connected；Equally, calcining furnace (2) and the second whirlwind point CaO outlets from device (8-2) are connected with carbonating stove (1) CaO entrances；First cyclone separator (8-1) and the second cyclonic separation Smoke inlet of the exhanst gas outlet of device (8-2) respectively with First Heat Exchanger (9-1) and the second heat exchanger (9-2) is connected.
2. a kind of carbon emission reduction system for coupling manufacture of cement and spent bleaching clay and recycling according to claim 1, its feature exist In the carbonating stove (1) is fluidized-bed reactor.
3. a kind of carbon emission reduction system for coupling manufacture of cement and spent bleaching clay and recycling according to claim 1, its feature exist In the calcining furnace (2) is fluidized-bed reactor.
4. a kind of carbon emission reduction system for coupling manufacture of cement and spent bleaching clay and recycling according to claim 1, its feature exist In the operating temperature range of the spent bleaching clay pyrolysis oven (3) is 500 DEG C~800 DEG C, and pyrolysis oven institute's calorific requirement is by partly circulating The sensible heat that pyrolysis gas carries provides, and pyrolysis gas internal circulating load is 10%~20%.
5. a kind of carbon emission reduction system for coupling manufacture of cement and spent bleaching clay and recycling according to claim 1, its feature exist In, the absorbent, mass component 85%CaCO3, 5% pyrolysis clay dregs, 10% cement.
6. a kind of carbon emission reduction system for coupling manufacture of cement and spent bleaching clay and recycling according to claim 1, its feature exist In, the granulator (4) be high speed wet granulator, in pelletization with deionized water make binding agent be granulated use it is natural Calcium-base absorbing agent is lime stone or dolomite, is pyrolyzed clay dregs and cement additive amount and is all no more than 20%.
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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN108579666A (en) * 2018-05-14 2018-09-28 东南大学 A method of preparing dearsenification adsorbent using spent bleaching clay
CN110801730A (en) * 2018-08-06 2020-02-18 黄有进 Carbon dioxide adsorption system
CN112390552A (en) * 2019-08-12 2021-02-23 天津水泥工业设计研究院有限公司 Cement predecomposition kiln system capable of realizing calcium circulation and method for preparing cement clinker
CN112390552B (en) * 2019-08-12 2023-07-07 天津水泥工业设计研究院有限公司 Cement predecomposition kiln system capable of realizing calcium circulation and method for preparing cement clinker
CN113606946A (en) * 2021-07-23 2021-11-05 中国中材国际工程股份有限公司 Carbon dioxide capture system and emission reduction method for cement kiln tail flue gas
CN116336464A (en) * 2023-04-07 2023-06-27 南京工程学院 Calcium-based hazardous waste synergistic trapping SO 2 /NO X /CO 2 Technological method and system
CN116336464B (en) * 2023-04-07 2024-01-19 南京工程学院 Calcium-based hazardous waste synergistic trapping SO 2 /NO X /CO 2 Technological method and system

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