WO2011000430A1 - Method and device for controlling a process for burning a lime containing mixture to burnt lime - Google Patents
Method and device for controlling a process for burning a lime containing mixture to burnt lime Download PDFInfo
- Publication number
- WO2011000430A1 WO2011000430A1 PCT/EP2009/058386 EP2009058386W WO2011000430A1 WO 2011000430 A1 WO2011000430 A1 WO 2011000430A1 EP 2009058386 W EP2009058386 W EP 2009058386W WO 2011000430 A1 WO2011000430 A1 WO 2011000430A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- kiln
- lime
- cavity
- temperature
- containing mixture
- Prior art date
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
- C04B2/00—Lime, magnesia or dolomite
- C04B2/10—Preheating, burning calcining or cooling
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
- F27B7/00—Rotary-drum furnaces, i.e. horizontal or slightly inclined
- F27B7/20—Details, accessories, or equipment peculiar to rotary-drum furnaces
- F27B7/42—Arrangement of controlling, monitoring, alarm or like devices
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D19/00—Arrangements of controlling devices
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F27—FURNACES; KILNS; OVENS; RETORTS
- F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
- F27D21/00—Arrangements of monitoring devices; Arrangements of safety devices
- F27D21/0021—Devices for monitoring linings for wear
Definitions
- the present invention refers to a method and a device for controlling a process for burning a lime containing mixture and converting it to burnt lime in a rotary kiln.
- the method is, for example, particularly useful in pulp mills ⁇ lime kilns) and in the cement industry.
- the process equipment includes a rotary kiln modelled as a tube reactor.
- the lime containing mixture is introduced in one end, also denoted cold-end, of the kiln and fuel mixed with air is introduced in the other end, also denoted hot- end.
- the moisture of the lime containing mixture is evaporated nearly totally during the process.
- a known problem for rotary kilns used for burning a lime containing mixture is the formation of rings on the inside perimeter of the kiln. Rings are formed when inert substances in the lime melt and then stick to the wall of the inside perimeter of the kiln. Rings can also be built up of evaporated substances, which condense on the inner wall closer to the cold end of the kiln. A high alkali content of the lime
- vapour condenses at a certain temperature (position) and rings tend to form at a certain position inside the perimeter of the kiln.
- One or more entrenchments can be built up at the same time depending on substances present and their concentrations. Behind such a ring, a "pool" of lime is built up and a natural flow of lime through the kiln is prevented.
- Another known problem is that mud balls are easily formed behind such a ring, which makes the burning of lime uneven and the result of this is unevenly burnt lime, i.e. large variations in the product quality and a far from optimum use of energy.
- Such rings and mud balls also cause inferior lime quality and can also interrupt the production of lime.
- Today, ring formations inside the kiln are commonly removed by shooting them away using guns. This causes an undesired interruption in the production of burnt lime.
- the method comprises collecting measurement data of the temperature in the wall at a plurality of measuring points along the longitudinal axis of the cavity, predicting the actual temperature gradient along the longitudinal axis of the cavity based at least on the measurement data of the temperature in the wall, and by means of a thermal model describing the temperature along the cavity of the kiln, determining a desired temperature gradient along the cavity based on the predicted temperature gradient along the cavity and a predetermined control strategy for controlling the temperature in the kiln so that the area of deposition of lime on the inside of the walls of the kiln is controlled and the drawbacks of the lime deposition is reduced.
- the temperature in the kiln varies along the length of the kiln.
- the temperature is highest at that end at which the burner is positioned (i.e. the hot-end) and the temperature decreases towards the end at which the lime mud is supplied (i.e. the cold-end).
- the ring formation is due to deposition of lime on the inside of the cavity and occurs at a certain temperature.
- the position of the ring formations depends on the temperature in the kiln. If the temperature is high and the residence time long enough, the deposited lime will start to sinter and form compounds that are insoluble in water.
- the actual temperature gradient along the longitudinal axis of the cavity of the kiln is predicted and a desired temperature gradient along the cavity is determined based on the predicted temperature and a predetermined control strategy.
- a control strategy is meant a strategy for controlling where the lime deposition takes place in the cavity in order to reduce the drawbacks that occur due to the lime deposition. It is difficult to reduce or prevent the lime deposition.
- it is possible to alleviate the consequences of the lime deposition by controlling where and how the lime deposition takes place in the cavity.
- the control of where and how the lime deposition takes place in the cavity is made by controlling the temperature in the cavity.
- the control strategy may also include rules for the maximum temperature in the area of deposition in the kiln in order to prevent sintering of the deposited lime.
- Set-point values for supply of lime containing mixture and fuel to obtain the desired temperature gradient is determined based on the desired temperature gradient and the predicted temperature in the kiln.
- area of deposition is meant the area of the wall of the cavity at which deposition of lime may occur due to the current temperature conditions in the kiln. Measuring the temperature inside the cavity is difficult. However, measuring the temperature in the wall of the kiln is much easier.
- the temperature inside the cavity is predicted based on a thermal model. The thermal model is adapted due to changing conditions over time by measuring the
- the method comprises collecting measurement data of the supply of lime containing mixture to the kiln, collecting measurement data of the supply of fuel to said burner, predicting the actual temperature gradient along the longitudinal axis of said cavity based on the supply of lime containing mixture and on the supply of fuel, and determining set-point values for supply of lime containing mixture and supply of fuel to obtain the desired temperature gradient.
- the control strategy is to keep the temperature in the area of deposition essentially at a constant level in order to concentrate the deposition of lime at a small area. If the temperature conditions in the kiln are very stable, the deposition of lime will be concentrated at a small area inside the cavity.
- the ring formation will become very thin and will break apart due to the transportation of lime mud through the kiln and/or due to its own weight. Thereby, undesired interruptions in the production of burnt lime due to ring formations in the cavity are reduced or even avoided.
- the control strategy controls the temperature in the kiln so that the temperature in the area of deposition is varied in order to spread out the lime deposition over a large area.
- the control strategy controls the temperature in the kiln so that the temperature at the area of deposition is kept below a predetermined value. Thereby, the risk that the deposited lime should sinter is reduced and the risk that the natural flow of lime through the kiln should be significantly affected or prevented is reduced.
- the control strategy controls the rotational speed of the rotary kiln in order to control the temperature and hence to control the deposition of inside the kiln.
- the method comprises
- the alkali content in the lime containing mixture supplied to the kiln is controlled by controlling the interruption of washing of the lime containing mixture. Thereby, the alkali content of the lime containing mixture is kept under control and hence the formation of rings, balls and dust can be reduced.
- the method comprises
- the method comprises measuring the electrical conductivity of filtrate from the washing and based thereon determining the alkali content of the lime containing mixture.
- the conductivity of the filtrate depends on the electrical conductivity in the water; high conductivity implies high alkali content and vice versa.
- the conductivity of the filtrate is quick and easy to measure, and accordingly this method for measuring the electrical conductivity of filtrate is quick and easy.
- the device comprises a plurality of sensors adapted to measure the temperature in the kiln, the sensors being arranged in the wall of the kiln at a plurality of positions along the longitudinal axis of the cavity, and a control unit configured to:
- the lime containing mixture is washed in a filter before being supplied to the kiln
- the device comprises an apparatus for measuring the electrical conductivity of the filtrate from the washing
- the control unit is configured to:
- Fig. 1 shows a device for controlling a process for burning a lime containing mixture (CaCOs) and converting it to calcinated lime (CaO) in a rotary kiln, according to an embodiment of the invention.
- Fig. 2a shows part of the cavity and how lime is deposited inside the kiln when the area of lime deposition is large.
- Fig. 2b shows part of the cavity and how lime is deposited inside the kiln when the area of lime deposition is small.
- Figure 1 shows a device 1 for controlling a process for burning a lime containing mixture (CaCOg) and converting it to calcinated lime (CaO) in a rotary kiln 2, according to an embodiment of the invention.
- the device 1 is arranged to be used in association with pulp mills (lime kilns) or in the cement industry.
- the device 1 comprises a rotary kiln 2 having an elongated cavity 3, comprising a plurality of volume elements, surrounded by a wall 4.
- the kiln 2 is a long steel tube lined with refractory bricks (not shown) and the length of the kiln 2 is typically 50-100 metres.
- the kiln 2 has a hot end 14 typically arranged with a burner 5 and means 17 for discharging burnt lime (CaO) from the cavity 3.
- the lime containing mixture (CaCOe), with more or less water and impurities or additions including alkali salts and/or silica (SiOg) is fed into the cavity 3 of the kiln 2 through charging means 8 by feeding means (not shown) such as a screw conveyor arranged at the cold-end 15 of the kiln 2.
- feeding means such as a screw conveyor arranged at the cold-end 15 of the kiln 2.
- First water is evaporated into gas phase and thereafter the solids are heated and CO 2 is stripped off. Later on the temperature increases and alkali salts are evaporated.
- the kiln 2 has an incline of a few degrees towards the hot-end 14 and is slowly rotated about the longitudinal axis 20 of the cavity 3.
- the burner 5, arranged to heat the cavity 3 of the kiln 2 with hot flue-gases is typically a gas or oil burner, but also other fuels such as bio fuels may be used.
- the lime containing mixture meets the hot flue-gases on its way through the cavity 3, and flue-gases and dust is discharged at the cold end 15 of the cavity 3 where dust is separated from the flue-gases in a particle filter (not shown).
- the device comprises a plurality of sensors 6a-c arranged in the wall 4 of the cavity 3, and adapted to measure the temperature in the kiln 2 at a plurality of different positions along the longitudinal axis 20 of the cavity 3.
- the device 1 also comprises a control unit 7, such as a computer or a PLC 1 arranged to the temperature in the kiln 2 according to a thermal model.
- the control unit 7 comprises a memory unit and a CPU and is configured to collect the temperature data in the cavity 3 of the kiln 2 measured by the sensors 6a-c.
- the control unit 7 is connected to the sensors 6a-c arranged in the wall 4 of the cavity 3, in order to collect temperature measurement data which is measured by the sensors 6a-c at a plurality of measuring points, in the wall 4, along the longitudinal axis 20 of the cavity 3. Further the control 7 is connected to the fuel pipe 9 of the burner 5 in order to regulate the fuel supply to the burner 5.
- the actual temperature gradient along the longitudinal axis 20 of the cavity 3 is predicted based at least on the measurement data of the temperature in the wall 4.
- the temperature along the cavity 3 of the kiln 2 is described by means of a thermal model and a desired temperature gradient along the cavity 3 is determined based on the predicted temperature gradient along the cavity 3.
- a predetermined control strategy controls the temperature in the kiln 2 so that the area of deposition 10 of lime on the inside of the walls 4 of the kiln 2 is controlled and hence the drawbacks of lime deposition 10 are reduced.
- the predetermined control strategy is based on previous experiences on how to control the temperature in the kiln 2.
- Washing of the lime containing mixture is performed in a filter 16 from which the lime containing mixture 13 is transported by transporting means (not shown) into the kiln 2. However, if washing is not performed no filter is used prior to the loading of lime containing mixture into the kiln 2.
- the lime alkali content in the lime containing mixture 13 is controlled by measuring the electrical conductivity of the filtrate 12 from the washing, and hence washing control is achieved. Thereby, it is possible to determine the alkali content of the lime containing mixture 13.
- Low washing efficiency causes high alkali content in the lime containing mixture 13 which prevents dust problems but causes problems with ring formation on the inside perimeter of the kiln 2.
- the washing of the lime containing mixture 13 is usually performed continuously but can also be performed batch wise.
- One or many sensors 19 are arranged in the filter 16 for the purpose of measuring the electrical
- Measurement data from the sensors 19 are processed in an apparatus 11 arranged for the purpose of determining the electrical conductivity of the filtrate 12 from the washing.
- the apparatus 11 is connected to the control unit 7. After washing the lime containing mixture is discharged from the filter 16 and eventually charged into the kiln 2 through the cold end 15.
- the alkali content is adjusted and controlled by measuring alkali in the filtrate 12, also known as waste-water or weak liquor.
- the concentration in the filtrate 12 is proportional to the content in the solid phase (CaCO 3 ).
- the alkali is controlled by adding specific additions, or by using a suitable mixture of bio fuels and other fuels, containing other ash components.
- the control unit 7 can use the temperature model to predict the material and energy balance along different parts of the kiln 2 along its length. This will give the temperature of solids, walls as well as gas components, along the kiln 2. Also the residence time at a specific temperature can be determined.
- the temperature model is controlled and adapted due to changing conditions with time by measuring the temperature at some positions along the lime kiln 2 through sensors, such as thermo couples, in the insulation ceramics i.e. the refractory bricks. This adaptation of the temperature model is important to obtain correct predictions.
- the temperature model is based on collected measurement data of the temperature in the wall 4 at a plurality of measuring points along the longitudinal axis 20 of the cavity 3. Thereby it is possible to predict the actual temperature gradient along the longitudinal axis 20 of the cavity 3 based at least on the measurement data of the temperature in the wall 4.
- a thermal model describes the temperature along the cavity 3 of the kiln 2 and thereby a desired temperature gradient along the cavity 3 can be determined based on the predicted temperature gradient along the cavity 3 and a predetermined control strategy controlling the temperature in the kiln 2.
- the temperature model also depends on collected measurement data of the supply of lime containing mixture to the kiln 2 and the supply of fuel to said burner 5.
- the temperature is primarily controlled by varying the fuel feed in relation to the feed of the lime containing mixture. Also, since fuel is mixed with air, the feed of air is controlled. However, this can also be combined with measuring the moisture content of the lime containing mixture and/or by varying the rotation speed of the kiln 2.
- the overall set-points for these actions are given by the temperature model combined with a number of local proportional-integral Pl-controls.
- Figure 2a shows when the predetermined control strategy controls the temperature in the kiln 21 so that the temperature in the area of deposition 23 in the kiln 21 is varied in order to spread out the lime deposition 23 over a large area.
- Figure 2b shows when the predetermined control strategy controls the temperature in the kiln 27 so that the temperature in the area of deposition 29 in the kiln 27 is kept essentially at a constant level in order to concentrate the deposition 29 of lime at a small area. If the temperature conditions in the kiln 27 are very stable, the deposition 29 of lime wilt be concentrated at a small area inside the cavity 31.
- the reactions are:
- the heat generated by the flames is given by:
- HHV is the higher heating value of the fuel mix. This means that if there are several fuels, the HHV is added for each fraction times the mass flow rate.
- An alternative control strategy is to implement a deliberate variation in dry solids content and kiln 2 temperature, e.g. sinoidal or similar, in order to obtain a varied temperature where the alkali vapour condensation occurs.
- the mixture of fuels e.g. sulphur content, heating value etc, can also be controlled and hence also the residence time of the flue-gases.
- the flow of additive chemicals should be closely controlled.
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Muffle Furnaces And Rotary Kilns (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Vertical, Hearth, Or Arc Furnaces (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN200980160281.4A CN102472582B (en) | 2009-07-03 | 2009-07-03 | Method and device for controlling a process for burning a lime containing mixture to burnt lime |
BR112012000103-5A BR112012000103B1 (en) | 2009-07-03 | 2009-07-03 | METHOD AND DEVICE FOR CONTROLLING A PROCESS OF BURNING A MIXING CONTAINING LIME FOR LIVE LIMES |
EP09780120.3A EP2449329B1 (en) | 2009-07-03 | 2009-07-03 | Method for controlling a process for burning a lime containing mixture to burnt lime |
PCT/EP2009/058386 WO2011000430A1 (en) | 2009-07-03 | 2009-07-03 | Method and device for controlling a process for burning a lime containing mixture to burnt lime |
US13/342,585 US8340825B2 (en) | 2009-07-03 | 2012-01-03 | Method and device for controlling a process for burning a lime containing mixture to burnt lime |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2009/058386 WO2011000430A1 (en) | 2009-07-03 | 2009-07-03 | Method and device for controlling a process for burning a lime containing mixture to burnt lime |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/342,585 Continuation US8340825B2 (en) | 2009-07-03 | 2012-01-03 | Method and device for controlling a process for burning a lime containing mixture to burnt lime |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2011000430A1 true WO2011000430A1 (en) | 2011-01-06 |
Family
ID=42112261
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2009/058386 WO2011000430A1 (en) | 2009-07-03 | 2009-07-03 | Method and device for controlling a process for burning a lime containing mixture to burnt lime |
Country Status (5)
Country | Link |
---|---|
US (1) | US8340825B2 (en) |
EP (1) | EP2449329B1 (en) |
CN (1) | CN102472582B (en) |
BR (1) | BR112012000103B1 (en) |
WO (1) | WO2011000430A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103307873A (en) * | 2013-06-26 | 2013-09-18 | 中冶长天国际工程有限责任公司 | Method for detecting flue-gas temperature in rotary kiln |
WO2019209156A1 (en) | 2018-04-23 | 2019-10-31 | Optimation Ab | Optimisation of control of rotary kiln |
EP3111151B1 (en) * | 2014-02-28 | 2020-04-01 | L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Method of operating an hydraulic-binder rotary-furnace |
US10995991B2 (en) | 2017-09-27 | 2021-05-04 | Andritz Inc. | Process for reducing ringing in lime kilns |
US11718559B2 (en) * | 2019-03-15 | 2023-08-08 | Gpcp Ip Holdings Llc | Closed loop control with camera detection of pebble size of lime particles to ameliorate lime kiln ringing and improve uptime and operating efficiency |
DE102018216446B4 (en) | 2017-10-16 | 2024-02-15 | Tcc Information Systems Corp. | Method for monitoring equipment by analyzing temperature values collected from a cylinder and distributed in a coordinate plane |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US8337757B2 (en) * | 2008-02-07 | 2012-12-25 | Precision Combustion, Inc. | Reactor control method |
EP2169483A1 (en) * | 2008-09-23 | 2010-03-31 | ABB Research Ltd | Method and system for controlling an industrial process |
US9121890B2 (en) | 2013-10-30 | 2015-09-01 | Globalfoundries Inc. | Planar metrology pad adjacent a set of fins of a fin field effect transistor device |
CN105330178B (en) * | 2015-11-10 | 2017-11-10 | 中信重工机械股份有限公司 | A kind of method that production active lime is transformed using cement producing line |
DE102016103937A1 (en) * | 2016-03-04 | 2017-09-07 | Maerz Ofenbau Ag | Oven and method of operating a furnace |
US10444079B2 (en) * | 2016-10-13 | 2019-10-15 | Tata Consultancy Services Limited | System and method for accretion detection |
Citations (2)
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US3273874A (en) * | 1963-12-12 | 1966-09-20 | Honeywell Inc | Controlling apparatus |
JPH11230676A (en) | 1998-02-16 | 1999-08-27 | Taiheiyo Cement Corp | Operation controller and control method for rotary kiln |
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DK424281A (en) * | 1981-09-25 | 1983-03-26 | Kemotron A S | METHOD OF MANAGING WHITE CHARACTERISTICS |
CN2093390U (en) * | 1990-04-29 | 1992-01-15 | 江西水泥厂 | Burnt zone temperature-measuring apparatus for cement rotary kiln |
US5213663A (en) * | 1991-07-22 | 1993-05-25 | The Foxboro Company | Method for controlling the sodium carbonate concentration of green liquor in the dissolving tank |
CN2366838Y (en) * | 1999-02-04 | 2000-03-01 | 浙江大学工业自动化工程研究中心 | Device for automatically and continuously measuring temp. in calcining rotary kiln |
CN2662215Y (en) * | 2003-11-28 | 2004-12-08 | 东华工程科技股份有限公司 | Rotary kiln materiel temperature detecting apparatus |
CN101464093A (en) * | 2007-12-19 | 2009-06-24 | 贵阳铝镁设计研究院 | Temperature field detection method and device of calcination rotary kiln |
-
2009
- 2009-07-03 BR BR112012000103-5A patent/BR112012000103B1/en active IP Right Grant
- 2009-07-03 WO PCT/EP2009/058386 patent/WO2011000430A1/en active Application Filing
- 2009-07-03 CN CN200980160281.4A patent/CN102472582B/en active Active
- 2009-07-03 EP EP09780120.3A patent/EP2449329B1/en active Active
-
2012
- 2012-01-03 US US13/342,585 patent/US8340825B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US3273874A (en) * | 1963-12-12 | 1966-09-20 | Honeywell Inc | Controlling apparatus |
JPH11230676A (en) | 1998-02-16 | 1999-08-27 | Taiheiyo Cement Corp | Operation controller and control method for rotary kiln |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103307873A (en) * | 2013-06-26 | 2013-09-18 | 中冶长天国际工程有限责任公司 | Method for detecting flue-gas temperature in rotary kiln |
CN103307873B (en) * | 2013-06-26 | 2015-07-29 | 中冶长天国际工程有限责任公司 | A kind of method detecting flue-gas temperature in kiln |
EP3111151B1 (en) * | 2014-02-28 | 2020-04-01 | L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Method of operating an hydraulic-binder rotary-furnace |
US10995991B2 (en) | 2017-09-27 | 2021-05-04 | Andritz Inc. | Process for reducing ringing in lime kilns |
DE102018216446B4 (en) | 2017-10-16 | 2024-02-15 | Tcc Information Systems Corp. | Method for monitoring equipment by analyzing temperature values collected from a cylinder and distributed in a coordinate plane |
WO2019209156A1 (en) | 2018-04-23 | 2019-10-31 | Optimation Ab | Optimisation of control of rotary kiln |
EP3784971A4 (en) * | 2018-04-23 | 2021-12-01 | Optimation AB | Optimisation of control of rotary kiln |
US11718559B2 (en) * | 2019-03-15 | 2023-08-08 | Gpcp Ip Holdings Llc | Closed loop control with camera detection of pebble size of lime particles to ameliorate lime kiln ringing and improve uptime and operating efficiency |
Also Published As
Publication number | Publication date |
---|---|
BR112012000103B1 (en) | 2017-10-31 |
CN102472582A (en) | 2012-05-23 |
BR112012000103A2 (en) | 2016-03-15 |
US20120143377A1 (en) | 2012-06-07 |
EP2449329B1 (en) | 2014-12-03 |
EP2449329A1 (en) | 2012-05-09 |
US8340825B2 (en) | 2012-12-25 |
CN102472582B (en) | 2014-05-07 |
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