CN107903921B - Carbon emission reduction system coupling cement production and spent bleaching clay recycling - Google Patents
Carbon emission reduction system coupling cement production and spent bleaching clay recycling Download PDFInfo
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- CN107903921B CN107903921B CN201711083562.7A CN201711083562A CN107903921B CN 107903921 B CN107903921 B CN 107903921B CN 201711083562 A CN201711083562 A CN 201711083562A CN 107903921 B CN107903921 B CN 107903921B
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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
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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
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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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
- B01D53/81—Solid phase processes
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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
- C04B7/24—Cements from oil shales, residues or waste other than slag
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- 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
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- 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
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- 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 invention discloses a carbon emission reduction system coupling cement production and waste clay recycling, which mainly comprises a carbonating furnace (1), a calcining furnace (2), a waste clay pyrolysis furnace (3), a granulator (4), a rotary kiln (5), a cooler (6), a flour mill (7), cyclone separators (8-1 and 8-2), heat exchangers (9-1 and 9-2) and the like; wherein the carbon capture system mainly comprises a carbonating furnace and a calcining furnace and is used for capturing CO in flue gas2(ii) a Pyrolysis gas generated by the waste clay pyrolysis furnace enters a calcining furnace to provide high-temperature conditions required by the regeneration of the calcium-based absorbent, and the cost input of a carbon capture system is reduced; mixing the pyrolyzed white clay residue with cement and calcined limestone powder to prepare a high-activity formed calcium-based absorbent, and feeding the formed calcium-based absorbent into a calcining furnace; the inactivated calcium-based absorbent discharged from the calcining furnace is used as a raw material for cement production to further reduce CO in a cement plant2And (4) discharging the amount.
Description
Technical Field
The invention relates to resource utilization of waste argil, cement production and cyclic CO capture of calcium2The technical combination belongs to the crossing field of cement production and environmental protection technology.
Background
In 2016, 11 months, the Paris convention for greenhouse control comes into effect formally, and China promises to realize CO 2030 years ago2Emission peaks and efforts are made to achieve this goal in advance, with the exception of coal-fired power plants, where cement production is the predominant CO2One of the emission sources is not only due to the high energy consumption in the cement production process, but also the contribution of the process of preparing the cement clinker by calcining limestone is over 50 percentCO of2And (4) discharging the amount. China is a big cement producing country, the cement yield of China in 2014 is 24.78 hundred million tons, the cement yield occupies 59 percent of the total cement yield of the whole world, and the cement yield contributes to 15 percent of the total carbon emission.
Post combustion CO capture2The technology is one of carbon emission reduction technologies with development prospects, wherein natural calcium-based absorbents (such as limestone, dolomite and the like) with low price and rich reserves are used in the calcium circulation method process, and the technology has certain economical efficiency. The calcium circulation system mainly comprises a calcination reactor and a carbonation reactor, wherein a calcium-based absorbent is arranged in the calcination reactor (temperature)>The calcining reaction is carried out at 900 ℃ to generate high-concentration CO2And CaO; high concentration of CO2The flow is subjected to subsequent heat exchange, compression and storage, CaO enters a carbonation reactor (the temperature is 650 ℃) to capture CO in the flue gas2Formation of CaCO3. So reciprocating, the absorbent carries out the circulating reaction in the system. The factors influencing the economy of the calcium circulation system mainly comprise two aspects: one is to maintain high temperature levels in the calciner, requiring the supply of additional fuel; secondly, the heat stability of the natural calcium-based absorbent is poor, the absorption performance is rapidly attenuated due to sintering in the circulation reaction, fresh absorbent needs to be continuously supplemented to maintain the required trapping capacity, and the material cost is increased. The inactivation absorbent discharged by the system can be used as a raw material for cement production, so that the overall economy of the system is improved. The economical efficiency of the calcium circulating system can be effectively improved by preparing or modifying the calcium-based absorbent by utilizing the solid waste. But based on the requirements of standard components of cement, the requirements are put forward on the components of the calcium-based absorbent modified substance so as to meet the subsequent cement production requirements.
Due to its high active surface area, activated clay is widely used in the refining of edible oils and lubricating oils. The oil content of the waste argil discharged in the refining process is up to 30%. According to statistics, the total yield of the edible oil and the lubricating oil in 2015 in China is 2743 and 372 ten thousand tons respectively, and at least 30 ten thousand tons of waste argil is generated by calculating the consumption of 1-6 wt.% of activated argil. Landfill is the main mode of handling spent bleaching clay at present, not only causes environmental pollution, has wasted the crude oil that adsorbs moreover. Regeneration of spent bleaching earth currently under investigationThe method mainly comprises heat treatment, acid solution treatment and supercritical CO2The recovery rate of the organic solvent extraction method is the highest, the recovery degree of the clay activity is the highest, but the process operation is complex, the cost is high, and the process economy is reduced.
Disclosure of Invention
The technical problem is as follows: in order to further improve the economy of the calcium circulation process and explore a new way for resource utilization of the waste argil, the invention provides a high-efficiency carbon capture system for coupling cement production and waste argil reutilization, fuel recovered from regenerated waste argil is used for partially or completely replacing high-value fuel used by a calcining reactor in the calcium circulation process, regenerated argil slag and cement are used for modifying a calcium-based absorbent, the sintering resistance of the absorbent is improved, the consumption of fresh absorbent is reduced, and the modified calcium-based absorbent meets the component requirement of cement production, so that the inactivated absorbent can be used as a raw material for cement production, and CO discharged by calcined limestone is reduced2Amount of the compound (A).
The invention content is as follows: in order to solve the technical problems, the invention provides a carbon emission reduction system coupling cement production and waste clay recycling, which mainly comprises a carbonating furnace, a calcining furnace, a waste clay pyrolysis furnace, a granulator, a rotary kiln, a cooler, a pulverizer, a first cyclone separator, a second cyclone separator, a first heat exchanger and a first heat exchanger; wherein the content of the first and second substances,
a pyrolysis gas outlet at the upper part of the waste argil pyrolysis furnace is connected with a fuel inlet of the calcining furnace, a bottom slag outlet of the waste argil pyrolysis furnace and a cement powder outlet of a cement mill of a cement plant are connected with a material inlet of a granulator, and a formed particle outlet of the granulator is connected with an absorbent inlet of the calcining furnace;
the discharge port of the inactivation absorbent in the calcining furnace is connected with the material inlet of the rotary kiln of the cement plant; a material outlet of the rotary kiln is connected with an inlet of a cooler, and an outlet of the cooler is connected with an inlet of the pulverizer;
a flue gas outlet of the rotary kiln is connected with a fluidized air inlet at the bottom of the carbonating furnace; CaCO of carbonating furnace and first cyclone3Export and calcinationCaCO of furnace3The inlets are connected; similarly, CaO outlets of the calcining furnace and the second cyclone separator are connected with a CaO inlet of the carbonating furnace; the flue gas outlets of the first cyclone separator and the second cyclone separator are respectively connected with the flue gas inlets of the first heat exchanger and the second heat exchanger.
The carbonation furnace is a fluidized bed reactor.
The calcining furnace is a fluidized bed reactor.
The working temperature range of the waste argil pyrolysis furnace is 500-800 ℃, the heat required by the pyrolysis furnace is provided by sensible heat carried by part of circulating pyrolysis gas, and the circulation amount of the pyrolysis gas is 10-20%.
The absorbent comprises 85% of CaCO by mass35% of pyrolytic white clay slag and 10% of cement.
The granulator is a high-speed wet granulator, the natural calcium-based absorbent used for granulation by using deionized water as a binder in the granulation process is limestone or dolomite, and the addition amount of the pyrolysis white clay residue and the cement is not more than 20%.
Has the advantages that:
1. explores a new way for the resource utilization of the waste argil, recycles the waste argil and captures CO by calcium circulation2The technology is combined, so that the use value of the waste argil is improved;
2. the fuel recovered by the regenerated spent bleaching clay is used for replacing high-value fuel consumed in a calcining reactor in a calcium circulating system, so that the fuel cost can be reduced; the regenerated spent bleaching clay and cement modified calcium-based absorbent has improved anti-sintering capability, and the consumption of fresh absorbent is reduced, so that the cost of the absorbent is reduced;
3. the inactivated calcium-based absorbent is used as a raw material for cement production, so that CO generated in preparation of clinker by calcining limestone can be effectively reduced2And (4) discharging the amount.
Drawings
FIG. 1 is a schematic view of the apparatus of the present invention.
The figure includes: the device comprises a carbonating furnace 1, a calcining furnace 2, a waste clay pyrolysis furnace 3, a granulator 4, a rotary kiln 5, a cooler 6, a flour mill 7, a first cyclone separator 8-1, a second cyclone separator 8-2, a first heat exchanger 9-1 and a second heat exchanger 9-2.
Detailed Description
The invention is explained in more detail below with reference to exemplary embodiments and the accompanying drawings. The following examples are not intended to limit the present invention in any way, and all technical solutions obtained by means of equivalent substitution or equivalent transformation are within the scope of the present invention.
In the invention, the waste clay regeneration technology, the cement production process and the calcium circulation method are used for capturing CO2The process is combined, so that high-value utilization of the waste argil can be realized, and the overall economy of the system is improved. The fuel (pyrolysis gas) recovered by the waste clay pyrolysis regeneration method enters the calciner to replace high-value fuel, and the high temperature of the calciner is maintained; the regenerated clay slag contains a certain amount of inert oxides and residual carbon, and is mixed with cement and calcined limestone powder to prepare a high-activity formed calcium-based absorbent, and the formed calcium-based absorbent enters a calciner to participate in cyclic calcination and carbonation reaction; the inactivated modified calcium-based absorbent discharged by the calcium circulating system meets the component requirements of cement production and is suitable for being used as a raw material for producing cement clinker, so that the share of CaO prepared by directly calcining limestone can be reduced, and the CO produced by the traditional cement production is reduced2And part of the discharged amount and finally produced cement is used for preparing high-activity absorbent particles, so that the coupling of a cement production process and a calcium circulation process is realized.
A pyrolysis gas outlet of the waste clay pyrolysis furnace 3 is connected with a fuel inlet of the calcining furnace 2, a bottom slag outlet of the waste clay pyrolysis furnace 3 and a cement powder outlet of a cement mill 7 of the cement plant are connected with a material inlet of the granulator 4, and a formed particle outlet of the granulator 4 is connected with an absorbent inlet of the calcining furnace 2; the working temperature range of the waste argil pyrolysis furnace is as follows; the regeneration method of waste clay comprises heat treatment, chemical treatment and supercritical CO2Extraction methods and organic solvent extraction methods; the energy required for maintaining high temperature in the calcining furnace is provided by oil, pyrolysis gas generated by regeneration of the waste argil, sensible heat of high-temperature flue gas generated by calcination and the like; the granulator can be a fluidized bed spray granulator, a high-speed wet granulator, an extrusion forming machine and the likeThe natural calcium-based absorbent used for mechanical and granulation is limestone or dolomite and the like.
The discharge port of the inactivation absorbent in the calcining furnace 2 is connected with the material inlet of the rotary kiln 5 of the cement plant; a material outlet of the rotary kiln 5 is connected with an inlet of a cooler 6, and an outlet of the cooler 6 is connected with an inlet of a pulverizer 7;
the flue gas outlet of the boiler and the rotary kiln 5 is connected with the fluidized air inlet at the bottom of the carbonator 1; CaCO of carbonator 1 and first cyclone 8-13CaCO of outlet and calciner 23The inlets are connected; similarly, CaO outlets of the calcining furnace 2 and the second cyclone separator 8-2 are connected with a CaO inlet of the carbonator 1; the flue gas outlets of the first cyclone separator 8-1 and the second cyclone separator 8-2 are respectively connected with the flue gas inlets of the first heat exchanger 9-1 and the second heat exchanger 9-2.
Aiming at the system provided by the invention, heat balance and material balance are roughly calculated, waste clay of a certain petrochemical refinery is taken as a sample, the oil content of the waste clay is 25-35% through experiment measurement, the oil content is 30% during calculation, the heat value of fuel oil is 10000kcal/kg, the combustion heat of the recovered oil content of 1kg of waste clay is 10000 4.18585 0.3-12557.6 kJ through calculation, the combustion heat calculated by the oil content in the waste clay replaces the combustion heat release of pyrolysis gas in a calcining furnace, and the CaCO entering the calcining furnace from a carbonating furnace is assumed to be3At 650 deg.C, heating to 900 deg.C, and decomposing at constant temperature to obtain CaCO3The thermochemical equation of the pyrolysis reaction is shown in the formula (1), the reaction heat is calculated by the Kirgov equation, the calculation equation is shown in the formula (2),
calculated Delta H of 209.6kJ/mol, i.e. 1kg of CaCO calcined3The required energy is 2096kJ, and the composition of the composite absorbent material is 80 percent CaCO310% of pyrolytic white clay residue/10% of cementExample, the energy Q required to calcine 1kg of composite absorbent granules was calculated as the average carbonation conversion of 50%12096 × 0.8 × 0.5 ═ 838.4 kJ; energy Q provided by pyrolysis gas generated corresponding to waste clay212557.6 × 0.1/0.7 ═ 1793.9 kJ. Due to Q2>Q1Under the assumed conditions, the pyrolysis white clay residue is completely used for preparing the absorbent, and the generated pyrolysis gas can completely provide the energy required by the two-time calcination decomposition of the absorbent. When a multi-cycle reaction is carried out, additional fuel is consumed to provide the required heat of calcination.
The experimental result of the trapping performance of the absorbent shows that the component is 85 percent CaCO3The best trapping performance of the composite absorbent granules of 5% of the pyrolitic white clay residue/10% of the cement, calculated as the average carbonation conversion of 50%, is the energy Q required for 1kg of composite absorbent granules1' -2096.85 0.5-890.5 kJ; energy Q provided by pyrolysis gas generated corresponding to waste clay2' -12557.6 × 0.05/0.7-897.0 kJ. Due to Q2’>Q1' under the above assumed conditions, the pyrolysis white clay residue is all used for preparing the absorbent, and the generated pyrolysis gas can completely provide the energy required by the single calcination decomposition of the absorbent. When a multi-cycle reaction is carried out, additional fuel is consumed to provide the required heat of calcination.
Claims (4)
1. A carbon emission reduction system coupling cement production and spent bleaching clay recycling is characterized by mainly comprising a carbonation furnace (1), a calcining furnace (2), a spent bleaching clay pyrolysis furnace (3), a granulator (4), a rotary kiln (5), a cooler (6), a flour mill (7), a first cyclone separator (8-1), a second cyclone separator (8-2), a first heat exchanger (9-1) and a first heat exchanger (9-2); wherein the content of the first and second substances,
a pyrolysis gas outlet at the upper part of the waste clay pyrolysis furnace (3) is connected with a fuel inlet of the calcining furnace (2), a bottom slag outlet of the waste clay pyrolysis furnace (3) and a cement powder outlet of a cement mill (7) of a cement plant are connected with a material inlet of the granulator (4), and a formed particle outlet of the granulator (4) is connected with an absorbent inlet of the calcining furnace (2);
the discharge port of the inactivation absorbent in the calcining furnace (2) is connected with the material inlet of the rotary kiln (5) of the cement plant; a material outlet of the rotary kiln (5) is connected with an inlet of a cooler (6), and an outlet of the cooler (6) is connected with an inlet of a pulverizer (7);
a flue gas outlet of the rotary kiln (5) is connected with a fluidized air inlet at the bottom of the carbonating furnace (1); CaCO of carbonator (1) and first cyclone (8-1)3CaCO at the outlet of the calciner (2)3The inlets are connected; similarly, CaO outlets of the calcining furnace (2) and the second cyclone separator (8-2) are connected with a CaO inlet of the carbonator (1); the flue gas outlets of the first cyclone separator (8-1) and the second cyclone separator (8-2) are respectively connected with the flue gas inlets of the first heat exchanger (9-1) and the second heat exchanger (9-2);
the carbonation furnace (1) is a fluidized bed reactor;
the calcining furnace (2) is a fluidized bed reactor.
2. The carbon emission reduction system coupling cement production and spent bleaching earth recycling according to claim 1, wherein the working temperature range of the spent bleaching earth pyrolysis furnace (3) is 500-800 ℃, the heat required by the pyrolysis furnace is provided by sensible heat carried by partial circulating pyrolysis gas, and the circulation amount of the pyrolysis gas is 10-20%.
3. The system of claim 1, wherein the absorbent comprises 85% CaCO by mass35% of pyrolytic white clay slag and 10% of cement.
4. The carbon emission reduction system coupling cement production and spent bleaching clay recycling according to claim 1, wherein the granulator (4) is a high-speed wet granulator, the natural calcium-based absorbent used for granulation by using deionized water as a binder in the granulation process is limestone or dolomite, and the addition amount of the pyrolysis white clay residue and the cement is not more than 20%.
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| CN108579666B (en) * | 2018-05-14 | 2020-08-11 | 东南大学 | Method for preparing dearsenization adsorbent by using spent bleaching clay |
| CN110801730A (en) * | 2018-08-06 | 2020-02-18 | 黄有进 | Carbon dioxide adsorption system |
| 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 |
| CN113606946B (en) * | 2021-07-23 | 2023-04-28 | 中国中材国际工程股份有限公司 | Carbon dioxide capturing system and emission reduction method for cement kiln tail flue gas |
| 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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