WO2002083591A1 - A process and a plant for the production of portland cement clinker - Google Patents

A process and a plant for the production of portland cement clinker Download PDF

Info

Publication number
WO2002083591A1
WO2002083591A1 PCT/CA2002/000517 CA0200517W WO02083591A1 WO 2002083591 A1 WO2002083591 A1 WO 2002083591A1 CA 0200517 W CA0200517 W CA 0200517W WO 02083591 A1 WO02083591 A1 WO 02083591A1
Authority
WO
WIPO (PCT)
Prior art keywords
ions
exhaust gas
cement
kiln
hydration
Prior art date
Application number
PCT/CA2002/000517
Other languages
French (fr)
Inventor
Jean-Marie Lalande
Anne Tremblay
Original Assignee
Co2 Solution Inc.
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 Co2 Solution Inc. filed Critical Co2 Solution Inc.
Priority to US10/474,930 priority Critical patent/US6908507B2/en
Priority to DE60221373T priority patent/DE60221373D1/en
Priority to CA002443222A priority patent/CA2443222C/en
Priority to EP02724060A priority patent/EP1377531B1/en
Publication of WO2002083591A1 publication Critical patent/WO2002083591A1/en

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
    • C04B7/364—Avoiding environmental pollution during cement-manufacturing
    • C04B7/367—Avoiding or minimising carbon dioxide emissions
    • 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
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • 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
    • B01D53/84—Biological processes
    • 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
    • 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
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
    • Y02P40/121—Energy efficiency measures, e.g. improving or optimising the production methods
    • 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
    • Y02P40/18—Carbon capture and storage [CCS]

Definitions

  • the present invention relates generally to the field of processes and apparatuses for the production of Portland cement clinker. More specifically, it concerns a process and a plant for the recovery and recycling of the carbon dioxide emissions from the production of Portland cement clinker.
  • Portland cement is made of lime, alumina, iron and silica. This mixture is pulverized and fused together by burning at high heat (more than 1,400°C) in a rotary kiln. Combining the resulting material, called “clinker”, with gypsum, results in the production of a fine powder known as Portland cement.
  • carbon dioxide emissions come from fossil fuel combustion and a calcination stage of limestone (CaC0 3 ).
  • Portland cement is the binding agent that enables the formation of concrete, which will also include aggregates, air and water.
  • Portland cement is the result of a chemical combination of calcium (usually from limestone), silica (clay, sand and shale), alumina (bauxite), iron (ore) and small amounts of various chemicals called admixtures to which gypsum is added at the last grinding in order to control the cement setting process.
  • the dry process kiln 70 % in the U.S.
  • the wet process kiln older
  • the first step is similar.
  • the raw materials are crushed for reduction to about 3 inches or smaller.
  • the raw materials, properly proportioned are then ground with water, thoroughly mixed in the form of slurry.
  • the dry process raw materials are ground and mixed in a dry state.
  • the slurry or the dry material is fed to a rotary kiln inclined slightly form the horizontal where it is heated to more than 1 ,400 °C.
  • a rotary kiln is frequently as much as 12 feet in diameter and 400 feet long.
  • the "raw meal” is fed into the higher end ofthe kiln and progresses to the lower end, moved by the rotation. On its way down, the “raw meal” is facing a burner blowing its flame under an upward forced draft.
  • the new substance called clinker
  • the heat is recuperated from the cooling of the red-hot clinker and returned to the kiln.
  • the clinker remains to be ground into fine powder to which some gypsum is added to form cement.
  • Concrete is then put in bags or carried in bulk to ready mix plants. Concrete is produced by mixing cement with fine (sand) or coarse aggregates (gravel or crushed stone) and water. Often, some chemicals are added to control setting time and plasticity.
  • the first important reaction to occur is the calcining of limestone (calcium carbonate CaC ⁇ 3) into lime (calcium oxide CaO) and carbon dioxide (CO2) at a temperature of 1 650 °F (900 °C).
  • the second reaction is the bonding of calcium oxide and silicates to form calcium silicates. Small amounts of calcium aluminate and calcium aluminoferrite are also formed. The relative proportions of these compounds determine the key properties of the resultant Portland cement and the type classification.
  • Cement Kiln Dust a fine granular material generated during cement production, is carried up by the combustion gases.
  • the CKD is normally removed and collected by an air pollution control system.
  • the collected CKD which is mainly made up of lime (CaO), K 2 0, S0 3 , silica (Si0 2 ) and alumina (AI 2 O3) may be returned into the process or stocked.
  • the net CKD refuse (excluding CKD regenerated during the process) output by 110 US cement plants is approximately 3,3 million tonnes per year.
  • CO2 emissions produced by cement production come from two sources:
  • one tonne of cement generates 0.5 tonne of CO2 from limestone conversion and about 0.35 tonne of CO 2 from the combustion of fossil products, for a total of 0.85 tonne of CO for each tonne of cement produced.
  • Patent DE4032557 suggests a method of handling aggregates and cement claiming improved energetic efficiency and in this way, preventing C0 2 discharge by cement fabrics.
  • Patent JP09-110485 uses absorption and volatilization of C0 2 to produce energy.
  • European patent WO9966260 advises reutilization of industrial exhaust gas, thus achieving improved combustion efficiency.
  • Japanese patent 10-130045 discloses cement waste recycling in the fabrication of regenerated cement, by the way claiming a reduction of C0 2 emissions in the environment.
  • combined recycling of C0 2 and manufacture residues is often invoked as a means for reducing cementous polluting waste (JP2000-239670; JP2000-119049; JP09-168775).
  • recycled solid materials can be directly used for carbon dioxide fixation of industrial gas exhausts.
  • JP10-314758 was conceived so that C0 2 from the gaseous effluent of ceramic industries can be eliminated by introduction of residual water in cement plants.
  • CA1143910 describes a method allowing the use of C0 2 from a waste flue gas and some waste material for manufacturing an asbestos free fibre reinforced cement.
  • a European untitled document (GB103290) also expects recycling of CO 2 for Portland cement manufacturing, in the same way as patent GB384060, which particularly uses a simple valve to isolate produced C0 2 from other flue gases during the process.
  • Patent JP2000-072981 suggests carbon black production by utilizing exhaust gas in cement production through C0 2 catalytic fixation whilst another (JP58-208117) allows for the manufacture of liquefied carbon dioxide from the waste gas of cement calcining kiln.
  • Patent JP06-263665 deals with catalytic hydrogenation of carbon dioxide gas exhausted from cement factories for the production of chemicals such as methane and methanol.
  • carbonic anhydrase has already been used for waste water treatment (US 6,110,370) and recently, for reducing C0 2 emissions in enzymatic photobiorectors (US 5,614,378).
  • Carbonic anhydrase is a highly reactive enzyme observed in most animal and vegetal species and thus, readily available.
  • Trachtenberg (US 6,143,556; CA 2222030) describes a system for gas processing with carbonic anhydrase without suggesting any specific application for cement fabrics.
  • Michigan University introduced a photobioreactor for the conversion of C0 2 with carbonic anhydrase, however destined to medical use as an artificial lung for life support (WO 9200380; US 5,614,378).
  • US patent 6,258,335 unveiled a catalytic process for carbon dioxide removal of ice exhaust by chemical fixation. This technology includes the optional use of carbonic anhydrase without particular consideration for cement plants.
  • US Patent (4,743,545) exposed a bioreactor with hollow beads including catalyst, the latter being carbonic anhydrase if needed.
  • US 4,602,987 and US 4,761,209 disclose a method for extraction and utilization of oxygen from fluids.
  • This system conceived for oxygen recovering especially includes a step for carbon dioxide removal by carbonic anhydrase ().
  • EP0991462; AU7753398; WO9855210; CA2291785 in the name of the Applicant propose a countercurrent packed column bioreactor for treating carbon dioxide.
  • carbonic anhydrase is used immobilized or in a free state.
  • An object of the present invention is to satisfy the above-mentioned need.
  • a process for producing cement clinker comprising the steps of: a) providing a mixture of ground calcareous materials and ground argillaceous materials; b) heating the mixture of step a) to a temperature sufficient to calcine and fuse the ground materials to form the cement clinker, and thereby producing an exhaust gas containing C0 2 ; c) catalysing the hydration of at least a portion of the C0 2 contained in the exhaust gas and producing a solution containing bicarbonate ions and hydrogen ions; and d) adding to the solution obtained in step c) metal ions, and adjusting the pH of the solution to precipitate a carbonate of said metal.
  • the process according to the invention allows the carbon dioxide emissions from the production of cement clinker to be greatly reduced and even eliminated by simply catalysing the hydration of CO 2 into a solution of bicarbonate ions and hydrogen ions.
  • the bicarbonate ions are then reacted with metals ions to precipitate a carbonated metal harmless to the environment.
  • the hydration is preferably performed in the presence of an enzyme capable of catalysing the hydration of dissolved CO 2 into hydrogen ions and bicarbonate ions.
  • the enzyme is preferably carbonic anhydrase or an analogue thereof.
  • the metal ions are Ca++ and the carbonate is CaCO 3 .
  • the process preferably comprises after step d), the step of: e) recycling the CaC0 3 obtained in step d) into the process by adding the CaC0 3 to the mixture of step a).
  • the ions Ca++ are preferably obtained from the dissolution of a material selected from the group consisting of CaCI 2 , cement kiln dust and sea salts.
  • step c) of catalisation comprises the steps of: feeding liquid H 2 O and at least a portion of the exhaust gas into a bioreactor containing therein a reaction chamber filled with said carbonic anhydrase immobilized on a support.
  • the process according to this preferred embodiment allows reduction of C0 2 emissions at the source through a recycling loop integrated into the cement plant.
  • the loop mainly consists of gas/liquid CO 2 packed column absorption catalyzed by an immobilized enzyme (carbonic anhydrase) for the subsequent production of calcium carbonate (CaC0 3 ).
  • the loop is completed when the calcium carbonate is used as first class raw material for the fabrication of Portland cement.
  • the process has the advantages of recycling the CO 2 into the process and providing a first class raw material for the production of the cement clinker.
  • the calcareous materials are preferably selected from the group consisting of limestone, marine shells and marl, and the argillaceous materials are preferably selected from the group consisting of clay, slate, sand, shale, and blast-furnace slags.
  • the mixture of step a) further comprises one or more material selected form the group consisting of aluminium, iron and chemical admixture.
  • a plant for producing cement clinker comprising: a kiln for burning raw materials suitable for producing cement clinker, the kiln having an inlet for receiving the raw materials, an outlet for discharging the cement clinker and a gas outlet for discharging an exhaust gas containing CO2.
  • the plant also comprises means for catalysing the hydration of the CO 2 contained in the exhaust gas into bicarbonate ions and hydrogen ions; and means for reacting the bicarbonate ions with metal ions to precipitate the carbonate of said metal.
  • the metal ions are preferably Ca++ and the carbonate is preferably CaC0 3 .
  • the plant preferably further comprises means for transferring the precipitate CaC0 3 into the inlet of the kiln.
  • the means for catalysing the hydration of the C0 2 comprises a bioreactor comprising a gas inlet for receiving at least a portion of the exhaust gas from the kiln; a liquid inlet for receiving an aqueous liquid, a reaction chamber in fluid communication with the gas inlet and the liquid inlet, the reaction chamber containing therein immobilized enzymes capable of catalysing the hydration of dissolved CO 2 into bicarbonate ions and hydrogen ions; and a liquid outlet in fluid communication with the reaction chamber for discharging a solution of bicarbonate ions and hydrogen ions.
  • the means for reacting the bicarbonate ions with metal ions is preferably a reaction reservoir.
  • the plant comprises cleansing means for cleansing the exhaust gas; means for transferring the exhaust gas from the kiln to the cleansing means; and means for transferring the clean exhaust gas from the cleansing means to the catalysing means.
  • Figure 1 is a schematic flow chart of a process according to the invention.
  • the process according to a preferred embodiment of the invention comprises a step where the CO2 emissions from the rotary kiln used in the cement production are transformed into bicarbonate ions by contacting the CO2 gas emissions with an aqueous liquid in a bioreactor containing enzymes capable of catalysing the hydration of CO2 into hydrogen and bicarbonate ions, and then reacting the bicarbonate ions with calcium ions so as to precipitate calcium carbonate (CaCO3) and recycling the same as a first class raw material in the rotary kiln used for producing the Portland cement clinker.
  • the enzyme used is preferably carbonic anhydrase, and it is used free or immobilized on an appropriate support. .
  • Gaseous C0 2 considered the greatest contributor to the greenhouse effect, comes from the respiration of living organisms, fuel combustion and certain chemical reactions such as fossil fuel reforming.
  • the CO 2 produced by the two latter sources may be enzymatically treated with the enzymatic system described in WO9855210 in the name of the applicant.
  • This enzymatic system is a process for the transformation of gaseous C0 2 into bicarbonate and hydrogen ions.
  • the transformation reaction usually a slow naturally occurring process, is catalyzed by an immobilized or free state enzyme in a specially made reactor.
  • the enzymatic process catalyzes the hydration of dissolved carbon dioxide.
  • the subsequent ionization equilibrium reaction produces bicarbonate and hydrogen ions.
  • the following equations describe the relevant process :
  • Equation 1 Hydration dissolved C0 2 - H 2 CO 3
  • Equation 2 Ionization : H 2 C0 3 - H + + HC0 3 " -> C0 3 2" + H +
  • the carbonate ions are precipitated with calcium ions or others into carbonated mineral form.
  • the plant (10) for the production of cement clinker comprises a kiln schematically represented as box (12) for burning raw materials suitable for producing cement clinker.
  • the raw materials comprise calcareous (lime-bearing) and argillaceous (claylike) materials.
  • the calcareous material may be quarried limestone, dredged marine shells or marl.
  • the argillaceous materials could be clay, slate, shale, or special blastfurnace slags.
  • the raw materials are preferably pulverized and handled either as wet suspension or as dry solids.
  • the plant of the invention may use a dry process or a wet process,
  • the dry process the pulverized materials are dried in a kiln drier and mixed in the proper proportion.
  • a wet process the materials are processed as a wet slurry.
  • the kiln (12) has an inlet (14) for receiving the raw materials, an outlet (16) for discharging the cement clinker and a gas outlet (18) connected to a chimney stack (19) for discharging an exhaust gas containing C0 2 .
  • the plant (10) further comprises a bioreactor (20) for catalysing the hydration of the CO2 contained in the exhaust gas into bicarbonate ions and hydrogen ions.
  • the biorector (20) is preferably as described in WO9855210 in the name ofthe applicant. It has a gas inlet (22) for receiving at least a portion of the exhaust gas, preferably all the exhaust gas from the kiln (10) and a liquid inlet (24) for receiving an aqueous liquid.
  • the bioreator (20) further includes a reaction chamber (26) in fluid communication with the gas inlet (22) and the liquid inlet (24), the reaction chamber (26) containing therein enzymes capable of catalysing the hydration of dissolved C0 2 (meaning aqueous CO 2 ) into bicarbonate ions and hydrogen ions.
  • the enzymes may be in a free state or it may be immozbilized on appropriate supports.
  • a liquid outlet (28) in fluid communication with the reaction chamber (26) is provided for discharging a solution of bicarbonate ions and hydrogen ions.
  • the plant (10) further comprises means, preferably a reaction reservoir (30), for reacting the bicarbonate ions obtained in the bioreactor (20) with metal ions to precipitate a carbonate of said metal.
  • the bicarbonate ions are reacted with Ca++ ions obtained by the dissolution in the reservoir (30) of a material selected from the group consisting of CaCI 2 , cement kiln dust and sea salts.
  • the precipitate obtained, CaC0 3 is advantageously recycled in the process as a raw material fed to the kiln (10).
  • the plant (10) in such as case comprises means for transferring the precipitate CaC0 3 into the inlet (14) ofthe kiln (10).
  • the precipitate could be transferred directly into the kiln by means of conventional piping and pump systems, or by means of any other transfer system known in the art.
  • the precipitate will preferably be dried before being transferred to the kiln (10).
  • the plant also preferably comprises cleansing means, such as a filter (32), for cleansing the exhaust gas coming from the ciment chimney (19) of kiln (10).
  • the filter (32) helps removing the CKD from the exhaust gas, which CDK may advantageously be used in the process for precipitating the CaC0 3 .
  • the plant (10) comprises means for transferring the exhaust gas from the kiln to the cleansing means, and means for transferring the clean exhaust gas from the cleansing means to the bioreactor (20).
  • These transfer means may be, for example, any appropriate conduct systems.
  • the process for producing cement clinker comprising the steps of: a) providing a mixture of ground calcareous materials and ground argillaceous materials as defined above; b) heating the mixture of step a) to a temperature sufficient to calcine and fuse the ground materials to form the cement clinker, and thereby producing an exhaust gas containing C0 2 ; c) catalysing the hydration of at least a portion of the C0 2 contained in the exhaust gas and producing a solution containing bicarbonate ions and hydrogen ions; and d) adding to the solution obtained in step c) metal ions, and adjusting the pH of the solution to precipitate a carbonate of said metal.
  • the solution containing biocarbonate ions is preferably reacted with a solution containing Ca++ ions so to form CaC0 3 which can be recycled into the process as a first class raw material.
  • the temperature sufficient to calcine and fuse the materials to form cement clinker is 1400°C or more, meaning substantially 1400°C or more.
  • the process initiates CO2 emissions from three different sources: two from combustion and the other from the breakdown of CaCO3 into CaO and CO2.
  • the proposed complementary process intends, first, to transform CO2 according to the following bioreaction:
  • Ca2 + calcium chloride (CaCl2), CKD, sea salts or others CaC03 will precipitate easily in an aqueous solution containing HCO3 " and Ca++ ions.
  • this CaCO"3 can be used as first class raw material in the cement production process.
  • the enzymes used in the bioreactor could be any enzyme capable of catalysing the hydration of CO2 into hydrogen ions and bicarbonate ions, for example, carbonic anhydrase or analogue thereof.
  • the calcium ions can be provided by using any chemical compound containing calcium and being capable of providing calcium ions in solution, for example, CaC , sea salt, cement kiln dust or others.
  • Tables 2 and 3 show preliminary results of leaching essays performed on Cement Kiln Dust plant refuse and subsequent precipitation of bicarbonate ions by addition of filtered leachate. Analyses of major ion concentrations during the first leaching essay with 50 g of CKD in 500 ml water are shown in table 2. The most concentrated ions are potassium, calcium, sodium and chlorides, whereas aluminium, magnesium and baryum are weakly concentrated. A leaching pH of 12.33 allowed for recovery of a small portion of calcium present in the refuse. In spite of the calcite formation potential of this solution being 1.9 g calcite per liter, this cation dissolution potential may be increased by the variation of experimental parameters such as the pH, the temperature, the solid-liquid contact time and the solid concentration per unit of volume of water. Table 2 Major ion concentrations in CDK refuse leachate
  • the precipitation of bicarbonate ions may also be achieved by the addition of external chemical salts, such as calcium chloride, magnesium chloride, baryum chloride, sea salt etc.
  • external chemical salts such as calcium chloride, magnesium chloride, baryum chloride, sea salt etc.
  • Carbonated precipitates of these metals (CaC0 3 - calcite, MgC0 3 - magnesite, BaC0 3 - witherite, CaMg(C0 3 )2 - dolomite and others) were obtained in laboratory essays their optimal precipitation pH determined.
  • calcite and witherite were obtained at a pH as low as 8 and the increase of pH did not affect the composition of the precipitate.
  • concentration in magnesite however is optimal at a pH between 10 and 11 only.
  • Precipitation by addition of sea salt is optimal at pH 10 but tends to form hydroxocomplexes with available cations at very alcaline pH.
  • the essays were carried out with solutions of 0.1 mol/L in cations and bicarbonates, which in theory correspond to 10 g/L calcite, 8.4 g/L magnesite and 19.7 g/L witherite.
  • the process may comprise, prior to feeding the bioreactor with the CO2 emissions, a treatment unit for purifying the CO2 emissions and removing waste particles from the same, such as dust, etc.

Abstract

A process is disclosed for producing cement clinker, comprising the steps of: a) providing a mixture of ground calcareous materials and ground argillaceous materials; b) heating the mixture of step a) to a temperature sufficient to calcine and fuse the ground materials to form the cement clinker, and thereby producing an exhaust gas containing CO2; c) catalysing the hydration of at least a portion of the CO2 contained in the exhaust gas and producing a solution containing bicarbonate ions and hydrogen ions; and d) adding to the solution obtained in step c) metal ions, and adjusting the pH of the solution to precipitate a carbonate of said metal. Preferably, the metal ions are Ca++ obtained from the dissolution of a material selected from the group consisting of CaCl¿2?, cement kiln dust and sea salts and the carbonate is CaCO3 which is advantageously recycled into the process by adding the CaCO3 to the mixture of step a). A cement plant for performing this process is also disclosed.

Description

A PROCESS AND A PLANT FOR THE PRODUCTION OF PORTLAND
CEMENT CLINKER
FIELD OF THE INVENTION
The present invention relates generally to the field of processes and apparatuses for the production of Portland cement clinker. More specifically, it concerns a process and a plant for the recovery and recycling of the carbon dioxide emissions from the production of Portland cement clinker.
BACKGROUND
Preserving the environment goes above all through the recognition of polluting agents, a list stretching out every year. Carbon dioxide is a by-product of many industrial chemical reactions and is considered polluting only of late. Until recently still, it was rather seen as a consequence of no gravity from the combustion of carbonated compounds such as coal and petroleum, or else, as a desired final product in the control of gaseous emissions.
Accumulation of evidences as to the participation of C02 in the greenhouse effect responsible for earth's global warming revealed a problematic of extreme urgency. On this account, international engagements proposed in Kyoto (Kyoto protocol, 1997) have commanded for active research in reducing greenhouse effect gases, particularly CO2.
Amongst the finger pointed industries, cement fabrics account for 8 % of the CO2 planetary anthropic emissions. Portland cement is made of lime, alumina, iron and silica. This mixture is pulverized and fused together by burning at high heat (more than 1,400°C) in a rotary kiln. Combining the resulting material, called "clinker", with gypsum, results in the production of a fine powder known as Portland cement. In the production process, carbon dioxide emissions come from fossil fuel combustion and a calcination stage of limestone (CaC03). Portland cement is the binding agent that enables the formation of concrete, which will also include aggregates, air and water.
Portland cement is the result of a chemical combination of calcium (usually from limestone), silica (clay, sand and shale), alumina (bauxite), iron (ore) and small amounts of various chemicals called admixtures to which gypsum is added at the last grinding in order to control the cement setting process.
The production of one tonne of cement (2000) requires close to 3 500 tonnes of raw materials. Lime and silica account for approximately 85 % of the weight.
Two main categories of production processes are in use in this industry : the dry process kiln (70 % in the U.S.) and the wet process kiln (older). For both processes, the first step is similar. The raw materials are crushed for reduction to about 3 inches or smaller. In the wet process, the raw materials, properly proportioned, are then ground with water, thoroughly mixed in the form of slurry. In the dry process, raw materials are ground and mixed in a dry state. In both processes, the slurry or the dry material is fed to a rotary kiln inclined slightly form the horizontal where it is heated to more than 1 ,400 °C.
A rotary kiln is frequently as much as 12 feet in diameter and 400 feet long.
The "raw meal" is fed into the higher end ofthe kiln and progresses to the lower end, moved by the rotation. On its way down, the "raw meal" is facing a burner blowing its flame under an upward forced draft.
At the lower end, the new substance, called clinker, is formed in pieces about the size of marbles. The heat is recuperated from the cooling of the red-hot clinker and returned to the kiln. The clinker remains to be ground into fine powder to which some gypsum is added to form cement.
Cement is then put in bags or carried in bulk to ready mix plants. Concrete is produced by mixing cement with fine (sand) or coarse aggregates (gravel or crushed stone) and water. Often, some chemicals are added to control setting time and plasticity.
The first important reaction to occur is the calcining of limestone (calcium carbonate CaCθ3) into lime (calcium oxide CaO) and carbon dioxide (CO2) at a temperature of 1 650 °F (900 °C).
The second reaction is the bonding of calcium oxide and silicates to form calcium silicates. Small amounts of calcium aluminate and calcium aluminoferrite are also formed. The relative proportions of these compounds determine the key properties of the resultant Portland cement and the type classification.
Cement Kiln Dust (CKD)
Cement Kiln Dust (CKD), a fine granular material generated during cement production, is carried up by the combustion gases. The CKD is normally removed and collected by an air pollution control system. The collected CKD which is mainly made up of lime (CaO), K20, S03, silica (Si02) and alumina (AI2O3) may be returned into the process or stocked.
The US Environmental Protection Agency published a report on the forseeable costs of conforming to future regulations on CDK dust (EPA, 1998). Among the interesting information published in this report, is the ratio of CDK production relative to clinker production depending on Kiln type (Table 1). As it can be appreciated, wet processes generate a greater production of CKD (between 11 and 17 %).
Table 1 Average CKD production vs clinker production depending on Kiln type
Figure imgf000004_0001
Figure imgf000005_0001
The net CKD refuse (excluding CKD regenerated during the process) output by 110 US cement plants is approximately 3,3 million tonnes per year.
In the above-mentioned EPA study, the baselines and the costs relating to conforming to future regulations were calculated for every affected plant. The total before-tax baseline costs, the inital conformity costs and the annual conformity costs respectively amount to 54,9; 98,5 and 43,7 millions US$. Out of 110 US plants, 68 (62 %) would incur average annual costs of 646 000 US$, translating to 19,96 US$ per CKD tonne and 1,12 US$ per cement tonne produced. The total annual income for these 68 cement plants is estimated at 2,945 billion US$. The cost of conforming to regulations would therefore represent 1 ,5 % of their income.
CO2 emissions from cement Portland production
CO2 emissions produced by cement production come from two sources:
1. Fossil fuel combustion required to heat the raw meal - 6 millions BTUs/tonne of cement produce % tonne of Cθ2-
2. Calcining of limestone into lime - Vz tonne of Cθ2/tonne of cement.
In Canada, one tonne of cement generates 0.5 tonne of CO2 from limestone conversion and about 0.35 tonne of CO2 from the combustion of fossil products, for a total of 0.85 tonne of CO for each tonne of cement produced.
The very high temperatures required for cement production allow for burning all sorts of materials such as solvents, paint, and tires. At these temperatures, the combustion is complete and pollution is reduced to a minimum. The methods already known in the art for reducing C02 emissions are the improvement of the energy efficiency of the process, the replacement of high carbon fuels by low carbon fuels, the use of waste as alternative fuel, the use of industrial waste containing lime and the use of fly ash to replace cement (15 to 35 %) in concrete. Fly ash is a by-product of the combustion of pulverized coal in thermal power plants.
Literature abounds with a good number of processes destined to reducing carbon dioxide emissions by the cement industry. US6,240,859; GB587101; US5,744,078 propose above all an improvement of combustion efficiencies and recycling of fly ashes as cement additive. Patent DE4032557 suggests a method of handling aggregates and cement claiming improved energetic efficiency and in this way, preventing C02 discharge by cement fabrics. Patent JP09-110485 uses absorption and volatilization of C02 to produce energy. Finally, European patent WO9966260 advises reutilization of industrial exhaust gas, thus achieving improved combustion efficiency.
Japanese patent 10-130045 discloses cement waste recycling in the fabrication of regenerated cement, by the way claiming a reduction of C02 emissions in the environment. As a matter of fact, combined recycling of C02 and manufacture residues is often invoked as a means for reducing cementous polluting waste (JP2000-239670; JP2000-119049; JP09-168775). In some configurations (US6, 187,277; JP07-068164; JP2000-300983), recycled solid materials can be directly used for carbon dioxide fixation of industrial gas exhausts. Another Japanese patent (JP10-314758) was conceived so that C02 from the gaseous effluent of ceramic industries can be eliminated by introduction of residual water in cement plants.
CA1143910 describes a method allowing the use of C02 from a waste flue gas and some waste material for manufacturing an asbestos free fibre reinforced cement. A European untitled document (GB103290) also expects recycling of CO2 for Portland cement manufacturing, in the same way as patent GB384060, which particularly uses a simple valve to isolate produced C02 from other flue gases during the process.
Another way of reducing industrial C02 emissions consists of transforming this gas to synthesis products of commercial value. Patent JP2000-072981 suggests carbon black production by utilizing exhaust gas in cement production through C02 catalytic fixation whilst another (JP58-208117) allows for the manufacture of liquefied carbon dioxide from the waste gas of cement calcining kiln. Patent JP06-263665 deals with catalytic hydrogenation of carbon dioxide gas exhausted from cement factories for the production of chemicals such as methane and methanol.
A totally different approach preaches cement admixtures and compositions giving low loads on the environment and discharging smaller amounts of carbon dioxide, as it is the case for patents FR2669918 and JP2001 -039751.
Currently, many scripts emanate from scientists with the purpose of reducing C02 emissions in general. Sinking C02 in the seawater over the deep ocean floor (US 5,364,611 ; US 5,304,356; US 5,293,751) persists amongst the main considerations despite the many uncertainties and inconveniences associated with this method. Chemical fixation (CA 2352969) and selective adsorption of C02 (US 5,667,561 ; JP02-000699) also stand amongst favoured methods in the literature. Membrane separation (JP11-235999) and chemical conversion in ether or methanol (US 6,248,795) offer interesting possibilities as well. One cannot help, but conclude exhaust gas absorption (US6, 117,404; CA2255287; US5,888,256) remains one of the most promising methods and the very solubilization of concerned gases constitute the corner stone of all innovations in that field.
With this perspective, carbonic anhydrase has already been used for waste water treatment (US 6,110,370) and recently, for reducing C02 emissions in enzymatic photobiorectors (US 5,614,378). Carbonic anhydrase is a highly reactive enzyme observed in most animal and vegetal species and thus, readily available. Trachtenberg (US 6,143,556; CA 2222030) describes a system for gas processing with carbonic anhydrase without suggesting any specific application for cement fabrics. Michigan University introduced a photobioreactor for the conversion of C02 with carbonic anhydrase, however destined to medical use as an artificial lung for life support (WO 9200380; US 5,614,378).
US patent 6,258,335 unveiled a catalytic process for carbon dioxide removal of ice exhaust by chemical fixation. This technology includes the optional use of carbonic anhydrase without particular consideration for cement plants. US Patent (4,743,545) exposed a bioreactor with hollow beads including catalyst, the latter being carbonic anhydrase if needed.
US 4,602,987 and US 4,761,209 disclose a method for extraction and utilization of oxygen from fluids. This system conceived for oxygen recovering especially includes a step for carbon dioxide removal by carbonic anhydrase ().
EP0991462; AU7753398; WO9855210; CA2291785 in the name of the Applicant propose a countercurrent packed column bioreactor for treating carbon dioxide. In this process, carbonic anhydrase is used immobilized or in a free state.
Although a great deal of efforts have been made to reduce in general, the greenhouse effect caused by the emissions of C02, there is still a need for further improvements and that mainly in the field of cement clinker production.
SUMMARY OF THE INVENTION
An object of the present invention is to satisfy the above-mentioned need.
According to the present invention, there is provided a process for producing cement clinker, comprising the steps of: a) providing a mixture of ground calcareous materials and ground argillaceous materials; b) heating the mixture of step a) to a temperature sufficient to calcine and fuse the ground materials to form the cement clinker, and thereby producing an exhaust gas containing C02; c) catalysing the hydration of at least a portion of the C02 contained in the exhaust gas and producing a solution containing bicarbonate ions and hydrogen ions; and d) adding to the solution obtained in step c) metal ions, and adjusting the pH of the solution to precipitate a carbonate of said metal.
As can be appreciated, the process according to the invention allows the carbon dioxide emissions from the production of cement clinker to be greatly reduced and even eliminated by simply catalysing the hydration of CO2 into a solution of bicarbonate ions and hydrogen ions. The bicarbonate ions are then reacted with metals ions to precipitate a carbonated metal harmless to the environment.
The hydration is preferably performed in the presence of an enzyme capable of catalysing the hydration of dissolved CO2 into hydrogen ions and bicarbonate ions. The enzyme is preferably carbonic anhydrase or an analogue thereof.
Also preferably, the metal ions are Ca++ and the carbonate is CaCO3. In such a case, the process preferably comprises after step d), the step of: e) recycling the CaC03 obtained in step d) into the process by adding the CaC03 to the mixture of step a). Also in this case, the ions Ca++ are preferably obtained from the dissolution of a material selected from the group consisting of CaCI2, cement kiln dust and sea salts.
According to another preferred aspect, step c) of catalisation comprises the steps of: feeding liquid H2O and at least a portion of the exhaust gas into a bioreactor containing therein a reaction chamber filled with said carbonic anhydrase immobilized on a support.
As can be appreciated, the process according to this preferred embodiment allows reduction of C02 emissions at the source through a recycling loop integrated into the cement plant. The loop mainly consists of gas/liquid CO2 packed column absorption catalyzed by an immobilized enzyme (carbonic anhydrase) for the subsequent production of calcium carbonate (CaC03). The loop is completed when the calcium carbonate is used as first class raw material for the fabrication of Portland cement.
According to this preferred aspect, the process has the advantages of recycling the CO2 into the process and providing a first class raw material for the production of the cement clinker.
The calcareous materials are preferably selected from the group consisting of limestone, marine shells and marl, and the argillaceous materials are preferably selected from the group consisting of clay, slate, sand, shale, and blast-furnace slags.
Also preferably, the mixture of step a) further comprises one or more material selected form the group consisting of aluminium, iron and chemical admixture.
According to the present invention, there is also provided a plant for producing cement clinker, comprising: a kiln for burning raw materials suitable for producing cement clinker, the kiln having an inlet for receiving the raw materials, an outlet for discharging the cement clinker and a gas outlet for discharging an exhaust gas containing CO2. The plant also comprises means for catalysing the hydration of the CO2 contained in the exhaust gas into bicarbonate ions and hydrogen ions; and means for reacting the bicarbonate ions with metal ions to precipitate the carbonate of said metal.
The metal ions are preferably Ca++ and the carbonate is preferably CaC03. In such a case, the plant preferably further comprises means for transferring the precipitate CaC03 into the inlet of the kiln.
According to a preferred aspect of the invention, the means for catalysing the hydration of the C02 comprises a bioreactor comprising a gas inlet for receiving at least a portion of the exhaust gas from the kiln; a liquid inlet for receiving an aqueous liquid, a reaction chamber in fluid communication with the gas inlet and the liquid inlet, the reaction chamber containing therein immobilized enzymes capable of catalysing the hydration of dissolved CO2 into bicarbonate ions and hydrogen ions; and a liquid outlet in fluid communication with the reaction chamber for discharging a solution of bicarbonate ions and hydrogen ions.
The means for reacting the bicarbonate ions with metal ions is preferably a reaction reservoir.
Also preferably, the plant comprises cleansing means for cleansing the exhaust gas; means for transferring the exhaust gas from the kiln to the cleansing means; and means for transferring the clean exhaust gas from the cleansing means to the catalysing means.
The objects, advantages and other features of the present invention will become more apparent upon reading of the following non restrictive description of the preferred embodiment thereof, given for the purpose of exemplification only with reference to the accompanying drawings.
DESCRIPTION OF THE DRAWING
Figure 1 is a schematic flow chart of a process according to the invention.
DESCRIPTION OF A PREFERRED EMBODIMENT
The process according to a preferred embodiment of the invention comprises a step where the CO2 emissions from the rotary kiln used in the cement production are transformed into bicarbonate ions by contacting the CO2 gas emissions with an aqueous liquid in a bioreactor containing enzymes capable of catalysing the hydration of CO2 into hydrogen and bicarbonate ions, and then reacting the bicarbonate ions with calcium ions so as to precipitate calcium carbonate (CaCO3) and recycling the same as a first class raw material in the rotary kiln used for producing the Portland cement clinker. The enzyme used is preferably carbonic anhydrase, and it is used free or immobilized on an appropriate support. .
Gaseous C02, considered the greatest contributor to the greenhouse effect, comes from the respiration of living organisms, fuel combustion and certain chemical reactions such as fossil fuel reforming. The CO2 produced by the two latter sources may be enzymatically treated with the enzymatic system described in WO9855210 in the name of the applicant. This enzymatic system is a process for the transformation of gaseous C02 into bicarbonate and hydrogen ions. The transformation reaction, usually a slow naturally occurring process, is catalyzed by an immobilized or free state enzyme in a specially made reactor. The enzymatic process catalyzes the hydration of dissolved carbon dioxide. The subsequent ionization equilibrium reaction produces bicarbonate and hydrogen ions. The following equations describe the relevant process :
Equation 1 Hydration : dissolved C02 - H2CO3
Equation 2 Ionization : H2C03 - H+ + HC03 " -> C03 2" + H+
The carbonate ions, among others, are precipitated with calcium ions or others into carbonated mineral form.
Detailed description of a plant according to a preferred embodiment of the invention
Referring to figure 1 , the plant (10) for the production of cement clinker comprises a kiln schematically represented as box (12) for burning raw materials suitable for producing cement clinker. As commonly used in the production of cement clinker, the raw materials comprise calcareous (lime-bearing) and argillaceous (claylike) materials. The calcareous material may be quarried limestone, dredged marine shells or marl. The argillaceous materials could be clay, slate, shale, or special blastfurnace slags. As in a typical mill, the raw materials are preferably pulverized and handled either as wet suspension or as dry solids. The plant of the invention may use a dry process or a wet process, In the dry process, the pulverized materials are dried in a kiln drier and mixed in the proper proportion. In a wet process, the materials are processed as a wet slurry.
The kiln (12) has an inlet (14) for receiving the raw materials, an outlet (16) for discharging the cement clinker and a gas outlet (18) connected to a chimney stack (19) for discharging an exhaust gas containing C02. The plant (10) further comprises a bioreactor (20) for catalysing the hydration of the CO2 contained in the exhaust gas into bicarbonate ions and hydrogen ions. The biorector (20) is preferably as described in WO9855210 in the name ofthe applicant. It has a gas inlet (22) for receiving at least a portion of the exhaust gas, preferably all the exhaust gas from the kiln (10) and a liquid inlet (24) for receiving an aqueous liquid. Although any liquid containing water could be used, it is easier to simply use water. The bioreator (20) further includes a reaction chamber (26) in fluid communication with the gas inlet (22) and the liquid inlet (24), the reaction chamber (26) containing therein enzymes capable of catalysing the hydration of dissolved C02 (meaning aqueous CO2) into bicarbonate ions and hydrogen ions. The enzymes may be in a free state or it may be immozbilized on appropriate supports. A liquid outlet (28) in fluid communication with the reaction chamber (26) is provided for discharging a solution of bicarbonate ions and hydrogen ions.
The plant (10) further comprises means, preferably a reaction reservoir (30), for reacting the bicarbonate ions obtained in the bioreactor (20) with metal ions to precipitate a carbonate of said metal.
According to a preferred aspect , the bicarbonate ions are reacted with Ca++ ions obtained by the dissolution in the reservoir (30) of a material selected from the group consisting of CaCI2, cement kiln dust and sea salts. In such a case, the precipitate obtained, CaC03, is advantageously recycled in the process as a raw material fed to the kiln (10). As will be apparent for any person in the field, the plant (10) in such as case comprises means for transferring the precipitate CaC03 into the inlet (14) ofthe kiln (10). As for example, in a wet process, the precipitate could be transferred directly into the kiln by means of conventional piping and pump systems, or by means of any other transfer system known in the art. In a dry process, the precipitate will preferably be dried before being transferred to the kiln (10).
The plant also preferably comprises cleansing means, such as a filter (32), for cleansing the exhaust gas coming from the ciment chimney (19) of kiln (10). The filter (32) helps removing the CKD from the exhaust gas, which CDK may advantageously be used in the process for precipitating the CaC03. As apparent to any person in the art, in such a case, the plant (10) comprises means for transferring the exhaust gas from the kiln to the cleansing means, and means for transferring the clean exhaust gas from the cleansing means to the bioreactor (20). These transfer means may be, for example, any appropriate conduct systems.
Detailed Description of the process
As defined above, and referring to figure 1 , the process for producing cement clinker, comprising the steps of: a) providing a mixture of ground calcareous materials and ground argillaceous materials as defined above; b) heating the mixture of step a) to a temperature sufficient to calcine and fuse the ground materials to form the cement clinker, and thereby producing an exhaust gas containing C02; c) catalysing the hydration of at least a portion of the C02 contained in the exhaust gas and producing a solution containing bicarbonate ions and hydrogen ions; and d) adding to the solution obtained in step c) metal ions, and adjusting the pH of the solution to precipitate a carbonate of said metal.
The solution containing biocarbonate ions is preferably reacted with a solution containing Ca++ ions so to form CaC03 which can be recycled into the process as a first class raw material.
The temperature sufficient to calcine and fuse the materials to form cement clinker is 1400°C or more, meaning substantially 1400°C or more.
The current industrial process for cement production relies on the following chemical reactions : CaCOβ + Δ → CaO + CO2 CaO + Siθ2 + Δ «-» Cement
The process initiates CO2 emissions from three different sources: two from combustion and the other from the breakdown of CaCO3 into CaO and CO2. The proposed complementary process intends, first, to transform CO2 according to the following bioreaction:
CO2 + H2O enzyme -> H+ + HCO3"
Secondly, to set a reaction between the ion HCO3- and an ion such as calcium
(Ca2+) which can be found for example in calcium chloride (CaCl2), CKD, sea salts or others CaC03 will precipitate easily in an aqueous solution containing HCO3" and Ca++ ions.
Thirdly, this CaCO"3 can be used as first class raw material in the cement production process.
Estimates of the quantities involved are calculated using the molecular weights converted into tonnes.
CO2 (aq) + H2O enzyme → H+ + HC03 " (bicarbonate) tonnes : 441 181 1 161 t HCO3" -» CO32" + H+ (Carbonate) tonnes : 61 1 601 1 t
CaCl2 → Ca2+ + 2 CI" tonnes : 66 1 40 1 26 1
Ca2+ + CO3-2" → CaC03 tonnes : 401 601 1001 The flow chart of figure 1 is more explicit in showing the main steps occurring in the cement production. The three CO2 emissions are identified. Two important sources are related to the energy required to heat, while the other is due to the lime production (CaO). All these emissions proceed to the chimney stack (19).
Assuming the bioreactor (20) to be 100 % efficient, 44 tonnes of CO2 would produce 60 tonnes of carbonate ions. This amount of carbonate added to 66 tonnes of CaCl2 could generate 100 tonnes of CaCO3.
The enzymes used in the bioreactor could be any enzyme capable of catalysing the hydration of CO2 into hydrogen ions and bicarbonate ions, for example, carbonic anhydrase or analogue thereof.
The calcium ions can be provided by using any chemical compound containing calcium and being capable of providing calcium ions in solution, for example, CaC , sea salt, cement kiln dust or others.
Tables 2 and 3 show preliminary results of leaching essays performed on Cement Kiln Dust plant refuse and subsequent precipitation of bicarbonate ions by addition of filtered leachate. Analyses of major ion concentrations during the first leaching essay with 50 g of CKD in 500 ml water are shown in table 2. The most concentrated ions are potassium, calcium, sodium and chlorides, whereas aluminium, magnesium and baryum are weakly concentrated. A leaching pH of 12.33 allowed for recovery of a small portion of calcium present in the refuse. In spite of the calcite formation potential of this solution being 1.9 g calcite per liter, this cation dissolution potential may be increased by the variation of experimental parameters such as the pH, the temperature, the solid-liquid contact time and the solid concentration per unit of volume of water. Table 2 Major ion concentrations in CDK refuse leachate
Figure imgf000017_0001
Further essays permitted to validate the precipitation potential of carbonate ions by the addition of refuse leachate to a sodium bicarbonate solution. In these essays, the pH of the leachate was not ajusted, rather, amounts of solids from the refuse were simply added in a volume of distilled water. The refuse added to water was mixed with agitation for two hours on a mechanical table agitator at room temperature of 22 °C. Conductivity and pH measurements of the leachate were taken from samples before the precipitation step.
The following table shows the results of leaching essays by addition of 50, 100 and 500 g of CKD to 500 ml of pure water. Firstly, the final leaching pH of sample PR1 (50 g CKD /500 ml) was 12.56 and that of the previous essay with the same refuse:water ratio was 12.33. This could explain precipitation of the mass at 0.7 g/L which is slightly inferior to the 0.95 g/L precipitation potential of calcite (1.9 g/L/2; dilution factor) calculated according to the 0.019 mol Ca/L in the leachate. The solid mass increase in the volume of water (samples PR2 and PR3) allowed for an increase of the resulting precipitate mass although not in a proportional fashion. The very alcaline pH during leaching might explain this phenomenon. Even if the conductivity of sample PR3 is higher than for PR1 and PR2, the 0.25 g/L precipitate mass is much weaker than the others. Chemical analyses will allow characterization of solid samples. Finally, all samples showed an effervescence reaction upon addition of diluted hydrochloric acid, which indicates precipitation of carbonate ions. Electron microscopy analyses of the sample, as well as mineral identification through X-ray diffraction confirmed pure calcite precipitation into cubic crystals with an average edge or 5μm.
Table 3 Results of preliminary refuse leaching and bicarbonate ion precipitation essays
Figure imgf000018_0001
Consequently, recovery of C02 from the fabrication of cement and its transformation into bicarbonate ions in an enzymatic reactor, followed by the bicarbonate ion precipitation into calcite, through addition of leached refuse from cement plants as a source of calcium, and integration of the calcite as raw matter into the cement fabrication process allows for the recovery of C02 responsible for the greenhouse effect and climatic changes. The perpetuel cycle of the present invention therefore allows the elimination of CO2 emissions from cement plants into the atmosphere and the production of a reusable by-product in the cement fabrication process.
The precipitation of bicarbonate ions, resulting from the transformation of CO2, may also be achieved by the addition of external chemical salts, such as calcium chloride, magnesium chloride, baryum chloride, sea salt etc. Carbonated precipitates of these metals (CaC03 - calcite, MgC03 - magnesite, BaC03 - witherite, CaMg(C03)2 - dolomite and others) were obtained in laboratory essays their optimal precipitation pH determined.
For example, calcite and witherite were obtained at a pH as low as 8 and the increase of pH did not affect the composition of the precipitate. The concentration in magnesite however is optimal at a pH between 10 and 11 only. Precipitation by addition of sea salt is optimal at pH 10 but tends to form hydroxocomplexes with available cations at very alcaline pH. The essays were carried out with solutions of 0.1 mol/L in cations and bicarbonates, which in theory correspond to 10 g/L calcite, 8.4 g/L magnesite and 19.7 g/L witherite.
Experimentation permitted to obtain up to 9.7 g/L calcite, 6.9 g/L magnesite and 19.4 g/L witherite. With sea salt, the maximal precipitate mass obtained was 5.3 g/L halite (NaCI) by evaporation during sample drying, hydromagnesite (Mg5(Cθ3)4(OH)2.4H20), dolomite (CaMgC03)2 and aragonite (CaCO3).
Also preferably, the process may comprise, prior to feeding the bioreactor with the CO2 emissions, a treatment unit for purifying the CO2 emissions and removing waste particles from the same, such as dust, etc.
Although a preferred embodiment of the present invention has been described in detail herein and illustrated in the accompanying drawings, it is to be understood that the invention is not limited to this precise embodiment and that various changes and modifications may be effected therein without departing from the scope or spirit of the present invention.

Claims

WHAT IS CLAIMED IS:
1. A process for producing cement clinker, comprising the steps of: a) providing a mixture of ground calcareous materials and ground argillaceous 5 materials; b) heating the mixture of step a) to a temperature sufficient to calcine and fuse the ground materials to form the cement clinker, and thereby producing an exhaust gas containing C02; c) catalysing the hydration of at least a portion of the CO2 contained in the 0 exhaust gas and producing a solution containing bicarbonate ions and hydrogen ions; and d) adding to the solution obtained in step c) metal ions, and adjusting the pH of the solution to precipitate a carbonate of said metal.
5 2. A process as claimed in claim 1 , wherein said hydration is performed in the presence of an enzyme capable of catalysing the hydration of dissolved C02 into hydrogen ions and bicarbonate ions.
3. A process as claimed in claim 1 wherein, the metal ions are Ca++ and the o carbonate is CaCC>3.
4. A process as claimed in claim 3, comprising, after step d), the step of: e) recycling the CaCO3 obtained in step d) into the process by adding the CaC03 to the mixture of step a). 5
5. A process as claimed in claim 2, wherein the enzyme used in step c) is carbonic anhydrase or an analogue thereof.
6. A process as claimed in claim 5, wherein step c) comprises the steps of o -feeding liquid H20 and at least a portion of the exhaust gas into a bioreactor containing therein a reaction chamber filled with said carbonic anhydrase immobilized on a support.
7. A process as defined in claim 3, wherein the ions Ca++ are obtained from the dissolution of a material selected from the group consisting of CaCI2, cement kiln dust and sea salts.
5
8. A process as defined in claim 1 , wherein the calcareous materials are selected from the group consisting of limestone, marine shells and marl.
9. A process as defined in claim 1 wherein the argillaceous materials are selected 0 from the group consisting of clay, slate, sand, shale, and blast-furnace slags.
10. A process as claimed in claim 1 , wherein the mixture of step a) further comprises one or more material selected form the group consisting of aluminium, iron and chemical admixture. 5
1 . A process as claimed in claim 1 , wherein the metal ions is selected from the group consisting of Ca++, Mg++, Ba++, CaMg++ and Na+.
12. A process as claimed in claim 1 , comprising, prior to step c) of hydration, the step 0 of:
-cleansing the exhaust gas for removing waste particles.
13 A process as claimed in claim 1, wherein said temperature sufficient to calcine and fuse the ground materials is at least 1400°C. 5
14. A plant for producing cement clinker, comprising:
-a kiln for burning raw materials suitable for producing cement clinker, the kiln having an inlet for receiving the raw materials, an outlet for discharging the cement clinker and a gas outlet for discharging an exhaust gas containing CO2; o -means for catalysing the hydration of the C02 contained in the exhaust gas into bicarbonate ions and hydrogen ions; means for reacting the bicarbonate ions with metal ions to precipitate the carbonate of said metal.
15. A plant as claimed in claim 14, wherein said metal ions are Ca++ and the carbonate is CaC03 and wherein the plant further comprises: means for transferring the precipitate CaCO3 into the inlet of the kiln.
16. A plant as claimed in claim 14, wherein the means for catalysing the hydration of the CO2 comprises a bioreactor comprising : -a gas inlet for receiving at least a portion of the exhaust gas from the kiln;
-a liquid inlet for receiving an aqueous iiquid, -a reaction chamber in fluid communication with the gas inlet and the liquid inlet, the reaction chamber containing therein immobilized enzymes capable of catalysing the hydration of dissolved C02 into bicarbonate ions and hydrogen ions; and
- a liquid outlet in fluid communication with the reaction chamber for discharging a solution of bicarbonate ions and hydrogen ions.
17. A plant as claimed in claim 14, wherein the means for reacting the bicarbonate ions with metal ions is a reaction tank.
18. A plant as claimed in claim 14, comprising;
-cleansing means for cleansing the exhaust gas; -means for transferring the exhaust gas from the kiln to the cleansing means; and
-means for transferring the clean exhaust gas from the cleansing means to the catalysing means. .
PCT/CA2002/000517 2001-04-13 2002-04-12 A process and a plant for the production of portland cement clinker WO2002083591A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US10/474,930 US6908507B2 (en) 2001-04-13 2002-04-12 Process and a plant for the production of Portland cement clinker
DE60221373T DE60221373D1 (en) 2001-04-13 2002-04-12 METHOD AND DEVICE FOR PRODUCING CEMENT LINKERS
CA002443222A CA2443222C (en) 2001-04-13 2002-04-12 A process and a plant for the production of portland cement clinker
EP02724060A EP1377531B1 (en) 2001-04-13 2002-04-12 A process and a plant for the production of portland cement clinker

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US28332701P 2001-04-13 2001-04-13
US60/283,327 2001-04-13

Publications (1)

Publication Number Publication Date
WO2002083591A1 true WO2002083591A1 (en) 2002-10-24

Family

ID=23085492

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2002/000517 WO2002083591A1 (en) 2001-04-13 2002-04-12 A process and a plant for the production of portland cement clinker

Country Status (6)

Country Link
US (1) US6908507B2 (en)
EP (1) EP1377531B1 (en)
AT (1) ATE368015T1 (en)
CA (1) CA2443222C (en)
DE (1) DE60221373D1 (en)
WO (1) WO2002083591A1 (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007003013A1 (en) 2005-07-05 2007-01-11 Greensols Australia Pty Ltd Preparation and use of cationic halides, sequestration of carbon dioxide
WO2008059378A2 (en) * 2006-11-13 2008-05-22 Lafarge Sa Process for the production of cement
FR2921059A1 (en) * 2007-09-14 2009-03-20 Rech S Geol Et Minieres Brgm E Production of clinker, comprises preparing calcium oxide material by producing flue gases that are used for direct/indirect heating of reactor for decarbonation of calcium carbonate, and blending calcium oxide material to form the clinker
US7596952B2 (en) * 2002-09-27 2009-10-06 Co2 Solution Inc. Process and a plant for recycling carbon dioxide emissions from power plants into useful carbonated species
WO2009122140A2 (en) 2008-04-04 2009-10-08 Johnson Matthey Plc Process for preparing catalysts
WO2009136485A1 (en) * 2008-05-07 2009-11-12 三菱マテリアル株式会社 Method and apparatus for recovering co2 gas in cement production equipment
JP2009269784A (en) * 2008-05-07 2009-11-19 Mitsubishi Materials Corp Recovery method and recovery equipment of co2 gas in cement manufacturing facility
JP2009269785A (en) * 2008-05-07 2009-11-19 Mitsubishi Materials Corp Method and apparatus for recovering co2 gas in cement production equipment
JP2009292715A (en) * 2008-05-07 2009-12-17 Mitsubishi Materials Corp Method and apparatus for recovering co2 gas in cement production equipment
EP2476478A1 (en) * 2011-01-12 2012-07-18 Lafarge Process for carbon dioxide removal from a gas by contacting it with a solid
EP2481472A1 (en) * 2006-03-10 2012-08-01 Douglas C. Comrie Carbon dioxide sequestration process
RU2469969C2 (en) * 2006-11-09 2012-12-20 Л'Эр Ликид, Сосьете Аноним Пур Л'Этюд Э Л'Эксплуатасьон Де Проседе Жорж Клод Method of producing clinker with controlled co2 emission
WO2013026011A1 (en) * 2011-08-17 2013-02-21 Massachusetts Institute Of Technology Biologically catalyzed mineralization of carbon dioxide
CN115403286A (en) * 2021-05-28 2022-11-29 中国科学院大连化学物理研究所 Method for preparing clinker and CO-producing CO by using solid reducing agent to catalyze limestone to reduce and decompose
WO2023208755A1 (en) 2022-04-27 2023-11-02 Evonik Operations Gmbh Storage of carbon dioxide released from lime

Families Citing this family (72)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2394073A1 (en) * 2002-07-16 2004-01-16 Cascades Inc., Recherche Et Developpement Process for synthesizing precipitated calcium carbonate using an enzyme
US7607482B2 (en) 2005-09-09 2009-10-27 Halliburton Energy Services, Inc. Settable compositions comprising cement kiln dust and swellable particles
US7514056B2 (en) * 2005-02-07 2009-04-07 Co2 Solution Inc. Process and installation for the fractionation of air into specific gases
CA2554395C (en) * 2005-07-27 2013-10-08 Carmen Parent Gas purification apparatus and process using biofiltration and enzymatic reactions
US8555967B2 (en) 2005-09-09 2013-10-15 Halliburton Energy Services, Inc. Methods and systems for evaluating a boundary between a consolidating spacer fluid and a cement composition
US9023150B2 (en) 2005-09-09 2015-05-05 Halliburton Energy Services, Inc. Acid-soluble cement compositions comprising cement kiln dust and/or a natural pozzolan and methods of use
US7789150B2 (en) 2005-09-09 2010-09-07 Halliburton Energy Services Inc. Latex compositions comprising pozzolan and/or cement kiln dust and methods of use
US7743828B2 (en) 2005-09-09 2010-06-29 Halliburton Energy Services, Inc. Methods of cementing in subterranean formations using cement kiln cement kiln dust in compositions having reduced Portland cement content
US9051505B2 (en) 2005-09-09 2015-06-09 Halliburton Energy Services, Inc. Placing a fluid comprising kiln dust in a wellbore through a bottom hole assembly
US8297357B2 (en) 2005-09-09 2012-10-30 Halliburton Energy Services Inc. Acid-soluble cement compositions comprising cement kiln dust and/or a natural pozzolan and methods of use
US8950486B2 (en) 2005-09-09 2015-02-10 Halliburton Energy Services, Inc. Acid-soluble cement compositions comprising cement kiln dust and methods of use
US7607484B2 (en) 2005-09-09 2009-10-27 Halliburton Energy Services, Inc. Foamed cement compositions comprising oil-swellable particles and methods of use
US8505630B2 (en) 2005-09-09 2013-08-13 Halliburton Energy Services, Inc. Consolidating spacer fluids and methods of use
US8609595B2 (en) 2005-09-09 2013-12-17 Halliburton Energy Services, Inc. Methods for determining reactive index for cement kiln dust, associated compositions, and methods of use
US8505629B2 (en) 2005-09-09 2013-08-13 Halliburton Energy Services, Inc. Foamed spacer fluids containing cement kiln dust and methods of use
US8333240B2 (en) 2005-09-09 2012-12-18 Halliburton Energy Services, Inc. Reduced carbon footprint settable compositions for use in subterranean formations
US8327939B2 (en) 2005-09-09 2012-12-11 Halliburton Energy Services, Inc. Settable compositions comprising cement kiln dust and rice husk ash and methods of use
US8403045B2 (en) 2005-09-09 2013-03-26 Halliburton Energy Services, Inc. Settable compositions comprising unexpanded perlite and methods of cementing in subterranean formations
US9676989B2 (en) 2005-09-09 2017-06-13 Halliburton Energy Services, Inc. Sealant compositions comprising cement kiln dust and tire-rubber particles and method of use
US8281859B2 (en) 2005-09-09 2012-10-09 Halliburton Energy Services Inc. Methods and compositions comprising cement kiln dust having an altered particle size
US9809737B2 (en) 2005-09-09 2017-11-07 Halliburton Energy Services, Inc. Compositions containing kiln dust and/or biowaste ash and methods of use
US8672028B2 (en) 2010-12-21 2014-03-18 Halliburton Energy Services, Inc. Settable compositions comprising interground perlite and hydraulic cement
US9006155B2 (en) 2005-09-09 2015-04-14 Halliburton Energy Services, Inc. Placing a fluid comprising kiln dust in a wellbore through a bottom hole assembly
US8307899B2 (en) 2005-09-09 2012-11-13 Halliburton Energy Services, Inc. Methods of plugging and abandoning a well using compositions comprising cement kiln dust and pumicite
US9150773B2 (en) 2005-09-09 2015-10-06 Halliburton Energy Services, Inc. Compositions comprising kiln dust and wollastonite and methods of use in subterranean formations
US8522873B2 (en) 2005-09-09 2013-09-03 Halliburton Energy Services, Inc. Spacer fluids containing cement kiln dust and methods of use
AU2012200916B2 (en) * 2006-03-10 2013-06-27 C-Quest Technologies International Llc Carbon dioxide sequestration materials and processes
US20100209968A1 (en) * 2007-05-04 2010-08-19 Akermin, Inc. Immobilized enzymes and uses thereof
AU2008256636C1 (en) * 2007-05-24 2011-03-03 Arelac, Inc. Hydraulic cements comprising carbonate compounds compositions
US7753618B2 (en) 2007-06-28 2010-07-13 Calera Corporation Rocks and aggregate, and methods of making and using the same
WO2010074686A1 (en) * 2008-12-23 2010-07-01 Calera Corporation Low-energy electrochemical hydroxide system and method
US7744761B2 (en) 2007-06-28 2010-06-29 Calera Corporation Desalination methods and systems that include carbonate compound precipitation
US7993616B2 (en) 2007-09-19 2011-08-09 C-Quest Technologies LLC Methods and devices for reducing hazardous air pollutants
US7749476B2 (en) * 2007-12-28 2010-07-06 Calera Corporation Production of carbonate-containing compositions from material comprising metal silicates
US7754169B2 (en) * 2007-12-28 2010-07-13 Calera Corporation Methods and systems for utilizing waste sources of metal oxides
GB2460910B8 (en) 2007-12-28 2010-07-14 Calera Corp Methods of sequestering CO2.
US20100239467A1 (en) 2008-06-17 2010-09-23 Brent Constantz Methods and systems for utilizing waste sources of metal oxides
US7919064B2 (en) * 2008-02-12 2011-04-05 Michigan Technological University Capture and sequestration of carbon dioxide in flue gases
US7875163B2 (en) 2008-07-16 2011-01-25 Calera Corporation Low energy 4-cell electrochemical system with carbon dioxide gas
US7993500B2 (en) 2008-07-16 2011-08-09 Calera Corporation Gas diffusion anode and CO2 cathode electrolyte system
CN101910469A (en) 2008-07-16 2010-12-08 卡勒拉公司 Co2 utilization in electrochemical systems
CN101868806A (en) 2008-09-11 2010-10-20 卡勒拉公司 CO2 commodity trading system and method
KR20110087273A (en) 2008-09-29 2011-08-02 아커민 인코퍼레이티드 Process for accelerated capture of carbon dioxide
CN101990523B (en) 2008-09-30 2015-04-29 卡勒拉公司 Co2-sequestering formed building materials
US7939336B2 (en) 2008-09-30 2011-05-10 Calera Corporation Compositions and methods using substances containing carbon
US8869477B2 (en) 2008-09-30 2014-10-28 Calera Corporation Formed building materials
US7815880B2 (en) * 2008-09-30 2010-10-19 Calera Corporation Reduced-carbon footprint concrete compositions
AU2009287466B2 (en) * 2008-10-22 2010-09-16 Arelac, Inc. Reduced-carbon footprint concrete compositions
CA2694980C (en) * 2008-10-31 2011-09-20 Calera Corporation Non-cementitious compositions comprising co2 sequestering additives
US9133581B2 (en) 2008-10-31 2015-09-15 Calera Corporation Non-cementitious compositions comprising vaterite and methods thereof
WO2010081007A2 (en) * 2009-01-09 2010-07-15 Codexis, Inc. Carbonic anhydrase polypeptides and uses thereof
US8834688B2 (en) 2009-02-10 2014-09-16 Calera Corporation Low-voltage alkaline production using hydrogen and electrocatalytic electrodes
JP2012519076A (en) 2009-03-02 2012-08-23 カレラ コーポレイション Gas flow complex contaminant control system and method
TW201105406A (en) 2009-03-10 2011-02-16 Calera Corp Systems and methods for processing CO2
US8474387B2 (en) * 2009-06-08 2013-07-02 Flsmidth A/S Method and apparatus for incineration of combustible waste
US7993511B2 (en) 2009-07-15 2011-08-09 Calera Corporation Electrochemical production of an alkaline solution using CO2
AU2010281322B2 (en) * 2009-08-04 2016-06-16 Saipem S.P.A. Process for CO2 capture using micro-particles comprising biocatalysts
AU2010281323B2 (en) 2009-08-04 2015-09-03 Saipem S.P.A. Process for co2 capture using carbonates and biocatalysts
US20110091955A1 (en) * 2009-10-19 2011-04-21 Constantz Brent R Methods and systems for treating industrial waste gases
FR2951716B1 (en) * 2009-10-22 2013-03-08 Lafarge Sa COMPOSITION FOR CAPTURING CO2
AU2011272878B2 (en) 2010-06-30 2015-04-23 Codexis, Inc. Highly stable beta-class carbonic anhydrases useful in carbon capture systems
WO2012003277A2 (en) 2010-06-30 2012-01-05 Codexis, Inc. Highly stable beta-class carbonic anhydrases useful in carbon capture systems
AU2011272825A1 (en) 2010-06-30 2013-01-10 Codexis, Inc. Chemically modified carbonic anhydrases useful in carbon capture systems
WO2012018699A2 (en) 2010-07-31 2012-02-09 Myriant Corporation Improved fermentation process for the production of organic acids
DE102011001817A1 (en) 2011-04-05 2012-10-11 Thyssenkrupp Polysius Ag Method and plant for producing cement and precipitated calcium carbonate
WO2014039578A1 (en) 2012-09-04 2014-03-13 Blue Planet, Ltd. Carbon sequestration methods and systems, and compositions produced thereby
EP2912172B1 (en) 2012-10-29 2018-12-05 CO2 Solutions Inc. Techniques for co2 capture using sulfurihydrogenibium sp. carbonic anhydrase
US10203434B2 (en) 2013-03-15 2019-02-12 Blue Planet, Ltd. Highly reflective microcrystalline/amorphous materials, and methods for making and using the same
CA2890582C (en) 2014-08-27 2022-07-19 Normand Voyer Co2 capture methods using thermovibrio ammonificans carbonic anhydrase
US11712654B2 (en) * 2017-03-02 2023-08-01 Blue Planet Systems Corporation Direct air capture (DAC) carbon dioxide (CO2) sequestration methods and systems
CN111892313A (en) * 2020-08-27 2020-11-06 南京凯盛开能环保能源有限公司 System and method for purifying and trapping carbon dioxide suitable for cement kiln
CN115403314B (en) * 2022-09-13 2023-07-11 广东省科学院江门产业技术研究院有限公司 Negative carbon structure material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925534A (en) * 1972-09-04 1975-12-09 Woodall Duckham Ltd Treatment of cement kiln flue dust
DE3729695A1 (en) * 1986-09-05 1988-03-17 Passamaquoddy Tribe METHOD AND DEVICE FOR REMOVING OXIDES FROM THE EXHAUST GAS FLOW OF A CEMENT FURNACE AND SIMULTANEOUSLY PRODUCING USEFUL PRODUCTS HERE

Family Cites Families (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB103290A (en) 1916-01-07 1917-12-06 Ernst Waldemar Jungner Improved Process of Producing Alkali Carbonate and Hydraulic Cement from Alkaliferous Silicate Minerals.
GB384060A (en) 1931-11-16 1932-12-01 Hubert Alexander Gill Improvements in processes of and plants for burning cement, lime and like materials
GB587101A (en) 1945-01-03 1947-04-14 Arthur Gustav Guttmann Improvements in and relating to the curing of concrete or precast stone by means of carbon dioxide
AU541464B2 (en) 1978-08-04 1985-01-10 Csr Limited Manufacturing fibre reinforced building element
US4743545A (en) 1984-08-09 1988-05-10 Torobin Leonard B Hollow porous microspheres containing biocatalyst
DE3218232A1 (en) 1982-05-14 1984-02-09 Quittkat, Wolfram G., Dr.-Ing., 8183 Rottach-Egern Process for burning carbonate-type raw materials
JPS58208117A (en) 1982-05-27 1983-12-03 Showa Denko Kk Manufacture of liquefied carbon dioxide
US4602987A (en) 1984-09-24 1986-07-29 Aquanautics Corporation System for the extraction and utilization of oxygen from fluids
JPH02699A (en) 1987-10-24 1990-01-05 Seibu Gas Kk Removal of carbon dioxide and moisture from gas in town gas production process
EP0408979B1 (en) 1989-07-19 1998-01-21 Mitsubishi Jukogyo Kabushiki Kaisha Method and system for throwing carbon dioxide into the deep sea
EP0429154B1 (en) * 1989-11-21 1994-12-21 Mitsubishi Jukogyo Kabushiki Kaisha Method for the fixation of carbon dioxide and apparatus for the treatment of carbon dioxide
US5614378A (en) 1990-06-28 1997-03-25 The Regents Of The University Of Michigan Photobioreactors and closed ecological life support systems and artifificial lungs containing the same
WO1992000380A1 (en) 1990-06-28 1992-01-09 The Regents Of The University Of Michigan Photobioreactors and closed ecological life support systems and artificial lungs containing the same
DE4032557C2 (en) 1990-09-26 1996-10-02 Ruhrkohle Ag Containers for the transport and handling of building materials consisting essentially of aggregates and cement
FR2669918B3 (en) 1990-12-04 1993-02-19 Joseph Davidovits PROCESS FOR OBTAINING A GEOPOLYMER CEMENT, WITHOUT EMISSION OF CARBONIC GAS CO2 AND PRODUCTS OBTAINED BY THIS PROCESS.
JP3146216B2 (en) 1993-03-12 2001-03-12 工業技術院長 CO2 catalytic hydrogenation
JPH0768164A (en) 1993-09-03 1995-03-14 Kyoei Kogyo Kk Carbon dioxide fixing material and carbon dioxide fixing filter
CN1128502A (en) 1994-03-15 1996-08-07 罗林帕克阿施塔化学技术进出口公司 Pollution control method and device enabling complete removal of nitrogen oxides from combustion gases in combustion processes
US5667561A (en) 1995-01-26 1997-09-16 Agency Of Industrial Science & Technology, Ministry Of International Trade & Industry Method for selective separation of carbon dioxide from waste gas of combustion
EP0830196A4 (en) 1995-06-07 1999-03-24 Michael C Trachtenberg Enzyme systems for gas processing
CA2222030C (en) 1995-06-07 2007-05-29 Michael C. Trachtenberg Enzyme systems for gas processing
JPH09110485A (en) 1995-10-09 1997-04-28 Ishikawajima Harima Heavy Ind Co Ltd Cement production equipment
JPH09168775A (en) 1995-12-19 1997-06-30 Yasuo Arai Method for treating concrete waste material to reutilize the same as resources
JPH09262432A (en) 1996-03-29 1997-10-07 Kansai Electric Power Co Inc:The Method for recovering basic amine compound in waste gas of decarboxylation column
US5744078A (en) * 1996-09-03 1998-04-28 Dpd, Inc. Accelerated processing of cement-bonded particleboard and fiberboard
US5888256A (en) 1996-09-11 1999-03-30 Morrison; Garrett L. Managed composition of waste-derived fuel
JPH10130045A (en) 1996-10-24 1998-05-19 Mitsubishi Materials Corp Regeneratable concrete material and method for recycling waste concrete material made from this concrete material
US5766339A (en) * 1997-05-07 1998-06-16 Dravo Lime Company Process for producing cement from a flue gas desulfurization process waste product
JPH10314758A (en) 1997-05-19 1998-12-02 Kubota Corp Waste water treatment system for ceramic industry system waste water
GB9711439D0 (en) 1997-06-04 1997-07-30 Rogers Peter A Bioreactor for dioxide management
AU732808B2 (en) 1997-08-25 2001-05-03 Water Research Commission Treatment of water
KR100228748B1 (en) 1997-10-10 1999-11-01 김충섭 Method for producing methanol and dimethylether from carbondioxid
JPH11235999A (en) 1998-02-20 1999-08-31 Mitsubishi Heavy Ind Ltd Carbon dioxide separation device
KR19980065026A (en) 1998-06-17 1998-10-07 최세환 Coal, Oil, Gas Combination Boiler
JP2000072981A (en) 1998-08-28 2000-03-07 Shimadzu Corp Apparatus for producing carbon black by utilizing exhaust gas in cement production process
JP2000119049A (en) 1998-10-13 2000-04-25 Taiheiyo Cement Corp Production of cement
JP3248514B2 (en) 1998-10-29 2002-01-21 日本鋼管株式会社 How to reduce carbon dioxide emissions
CA2255287A1 (en) 1998-12-11 2000-06-11 Rupesh N. Pandey Carbon dioxide mitigation and utilization process via chemical fixation to valuable commodities
JP3543934B2 (en) 1999-02-17 2004-07-21 三菱マテリアル株式会社 How to recycle waste concrete
JP2000300983A (en) 1999-04-20 2000-10-31 Sekisui Chem Co Ltd Carbon dioxide gas absorbent and its preparation
US6187277B1 (en) * 1999-06-04 2001-02-13 Leon Kirschner Method for purifying gases
JP3765690B2 (en) 1999-07-28 2006-04-12 電気化学工業株式会社 Low environmental load cement admixture and cement composition
US6258335B1 (en) 1999-09-15 2001-07-10 Sanjoy Kumar Bhattacharya Conversion of carbon dioxide from ice exhausts by fixation
US6240859B1 (en) * 2000-05-05 2001-06-05 Four Corners Group, Inc. Cement, reduced-carbon ash and controlled mineral formation using sub- and supercritical high-velocity free-jet expansion into fuel-fired combustor fireballs

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3925534A (en) * 1972-09-04 1975-12-09 Woodall Duckham Ltd Treatment of cement kiln flue dust
DE3729695A1 (en) * 1986-09-05 1988-03-17 Passamaquoddy Tribe METHOD AND DEVICE FOR REMOVING OXIDES FROM THE EXHAUST GAS FLOW OF A CEMENT FURNACE AND SIMULTANEOUSLY PRODUCING USEFUL PRODUCTS HERE

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7596952B2 (en) * 2002-09-27 2009-10-06 Co2 Solution Inc. Process and a plant for recycling carbon dioxide emissions from power plants into useful carbonated species
EP1899043A1 (en) * 2005-07-05 2008-03-19 Greensols Australia Pty Ltd Preparation and use of cationic halides, sequestration of carbon dioxide
WO2007003013A1 (en) 2005-07-05 2007-01-11 Greensols Australia Pty Ltd Preparation and use of cationic halides, sequestration of carbon dioxide
EP1899043A4 (en) * 2005-07-05 2011-03-23 Greensols Australia Pty Ltd Preparation and use of cationic halides, sequestration of carbon dioxide
EP2481472A1 (en) * 2006-03-10 2012-08-01 Douglas C. Comrie Carbon dioxide sequestration process
RU2469969C2 (en) * 2006-11-09 2012-12-20 Л'Эр Ликид, Сосьете Аноним Пур Л'Этюд Э Л'Эксплуатасьон Де Проседе Жорж Клод Method of producing clinker with controlled co2 emission
WO2008059378A2 (en) * 2006-11-13 2008-05-22 Lafarge Sa Process for the production of cement
WO2008059378A3 (en) * 2006-11-13 2008-10-30 Lafarge Sa Process for the production of cement
US8252109B2 (en) 2006-11-13 2012-08-28 Lafarge Process for the production of cement
FR2921059A1 (en) * 2007-09-14 2009-03-20 Rech S Geol Et Minieres Brgm E Production of clinker, comprises preparing calcium oxide material by producing flue gases that are used for direct/indirect heating of reactor for decarbonation of calcium carbonate, and blending calcium oxide material to form the clinker
WO2009122140A2 (en) 2008-04-04 2009-10-08 Johnson Matthey Plc Process for preparing catalysts
WO2009122140A3 (en) * 2008-04-04 2009-12-03 Johnson Matthey Plc Process for preparing catalysts involving the regeneration of metal carbonate precipitants
AU2009232223B2 (en) * 2008-04-04 2013-02-14 Johnson Matthey Plc Process for preparing catalysts involving the regeneration of metal carbonate precipitants
RU2482918C2 (en) * 2008-04-04 2013-05-27 Джонсон Мэтти Плс Method of making catalysts comprising regeneration of metal carbonate agents
US8815191B2 (en) 2008-04-04 2014-08-26 Johnson Matthey Public Limited Company Process for preparing catalysts involving the regeneration of metal carbonate precipitants
CN102015568A (en) * 2008-05-07 2011-04-13 三菱综合材料株式会社 Method and apparatus for recovering co2 gas in cement production equipment
JP2009269784A (en) * 2008-05-07 2009-11-19 Mitsubishi Materials Corp Recovery method and recovery equipment of co2 gas in cement manufacturing facility
US9446984B2 (en) 2008-05-07 2016-09-20 Mitsubishi Materials Corporation Method and facility for recovering CO2 gas in cement manufacturing facility
KR20110021752A (en) * 2008-05-07 2011-03-04 미츠비시 마테리알 가부시키가이샤 Method and apparatus for recovering co2 gas in cement production equipment
JP2009292715A (en) * 2008-05-07 2009-12-17 Mitsubishi Materials Corp Method and apparatus for recovering co2 gas in cement production equipment
JP2009269785A (en) * 2008-05-07 2009-11-19 Mitsubishi Materials Corp Method and apparatus for recovering co2 gas in cement production equipment
KR101586107B1 (en) 2008-05-07 2016-01-15 미츠비시 마테리알 가부시키가이샤 Method and apparatus for recovering co2 gas in cement production equipment
WO2009136485A1 (en) * 2008-05-07 2009-11-12 三菱マテリアル株式会社 Method and apparatus for recovering co2 gas in cement production equipment
US8617506B2 (en) 2008-05-07 2013-12-31 Mitsubishi Materials Corporation Method and facility for recovering CO2 gas in cement manufacturing facility
CN103313772A (en) * 2011-01-12 2013-09-18 拉法基公司 Process for carbon dioxide removal from a gas by contacting it with a solid
WO2012095406A1 (en) * 2011-01-12 2012-07-19 Lafarge Process for carbon dioxide removal from a gas by contacting it with a solid
EP2476478A1 (en) * 2011-01-12 2012-07-18 Lafarge Process for carbon dioxide removal from a gas by contacting it with a solid
WO2013026011A1 (en) * 2011-08-17 2013-02-21 Massachusetts Institute Of Technology Biologically catalyzed mineralization of carbon dioxide
CN115403286A (en) * 2021-05-28 2022-11-29 中国科学院大连化学物理研究所 Method for preparing clinker and CO-producing CO by using solid reducing agent to catalyze limestone to reduce and decompose
WO2023208755A1 (en) 2022-04-27 2023-11-02 Evonik Operations Gmbh Storage of carbon dioxide released from lime

Also Published As

Publication number Publication date
EP1377531A1 (en) 2004-01-07
ATE368015T1 (en) 2007-08-15
CA2443222A1 (en) 2002-10-24
CA2443222C (en) 2009-09-15
DE60221373D1 (en) 2007-09-06
US6908507B2 (en) 2005-06-21
US20040129181A1 (en) 2004-07-08
EP1377531B1 (en) 2007-07-25

Similar Documents

Publication Publication Date Title
US6908507B2 (en) Process and a plant for the production of Portland cement clinker
Pan et al. An innovative approach to integrated carbon mineralization and waste utilization: A review
Mazzella et al. CO2 uptake capacity of coal fly ash: Influence of pressure and temperature on direct gas-solid carbonation
JP3954009B2 (en) Carbon dioxide immobilization method
TWI522163B (en) Carbon dioxide sequestration involving two-salt-based thermolytic processes
Ghacham et al. CO2 sequestration using waste concrete and anorthosite tailings by direct mineral carbonation in gas–solid–liquid and gas–solid routes
CA2866186C (en) Carbon dioxide chemical sequestration from industrial emissions by carbonation
EP3656750A2 (en) Use of carbon dioxide from and for cement
Mattila et al. Production of precipitated calcium carbonate from steel converter slag and other calcium-containing industrial wastes and residues
KR20110061546A (en) Production of carbonate-containing compositions from material comprising metal silicates
JP2004261658A (en) Method for absorbing/fixing carbon dioxide in combustion exhaust gas
RU2596930C2 (en) Reducing method for continuous extraction of calcium and producing precipitated calcium carbonate
JP2015508332A (en) Sequestration of carbon dioxide with pyrolysis process based on two kinds of salts
Chang et al. CO2 capture by using blended hydraulic slag cement via a slurry reactor
CN104609446A (en) Process for the joint production of sodium carbonate and sodium bicarbonate
Yoo et al. Review of contemporary research on inorganic CO2 utilization via CO2 conversion into metal carbonate-based materials
Kumar et al. Lime calcination
JP2023036636A (en) Production of low-carbon footprint magnetic material
Zaremba et al. Properties of the wastes produced in the semi-dry FGD installation
Pan et al. CO2 Mineralization and Utilization by a High-Gravity Carbonation Process: Past, Present, and Future
Anawar et al. Biogeochemical Processes for Carbonation and Neutralization of Alkaline Mining Waste, Recycling and Waste Management
Wu et al. Alkali-activated materials without commercial activators: a review
Chiang et al. Principles of accelerated carbonation reaction
Chenier et al. Chemicals from limestone
EA043813B1 (en) OBTAINING LOW-CARBON MAGNESIUM OXIDE

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TN TR TT TZ UA UG US UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 2443222

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 2002724060

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 10474930

Country of ref document: US

WWP Wipo information: published in national office

Ref document number: 2002724060

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP

WWG Wipo information: grant in national office

Ref document number: 2002724060

Country of ref document: EP