GB2115802A - Refractory lined vessel and method of use - Google Patents

Refractory lined vessel and method of use Download PDF

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Publication number
GB2115802A
GB2115802A GB08235054A GB8235054A GB2115802A GB 2115802 A GB2115802 A GB 2115802A GB 08235054 A GB08235054 A GB 08235054A GB 8235054 A GB8235054 A GB 8235054A GB 2115802 A GB2115802 A GB 2115802A
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GB
United Kingdom
Prior art keywords
weight
vessel
amount
binder
expressed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB08235054A
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GB2115802B (en
Inventor
Harold Edward Haigh
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tioxide Group Ltd
Original Assignee
Tioxide Group Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of GB2115802A publication Critical patent/GB2115802A/en
Application granted granted Critical
Publication of GB2115802B publication Critical patent/GB2115802B/en
Expired legal-status Critical Current

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Classifications

    • 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
    • F27B15/00—Fluidised-bed furnaces; Other furnaces using or treating finely-divided materials in dispersion
    • F27B15/02—Details, accessories, or equipment peculiar to furnaces of these types
    • F27B15/04—Casings; Supports therefor
    • F27B15/06—Arrangements of linings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1872—Details of the fluidised bed reactor
    • 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
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/06—Aluminous cements
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1218—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes
    • C22B34/1222—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by dry processes using a halogen containing agent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00477—Controlling the temperature by thermal insulation means
    • B01J2208/00495—Controlling the temperature by thermal insulation means using insulating materials or refractories
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00948—Uses not provided for elsewhere in C04B2111/00 for the fabrication of containers
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Structural Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Metallurgy (AREA)
  • Dispersion Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Abstract

A vessel for use in the chlorination of a titaniferous material having an outer shell-like retaining wall, inlet means for the material and outlet means for discharge of gaseous products with a base provided with a means to introduce a gas into the vessel and the shell-like retaining wall having a refractory lining and the base an infill material in which the lining, infill material and/or means to introduce a gas are formed of a refractory concrete containing an aggregate and a high alumina binder containing up to 20% by weight of calcium chloride. The chorinator vessel has been found to have a much improved life during use with the refractory concrete, the material being capable of withstanding the action of chlorine gas over extended periods. <IMAGE>

Description

SPECIFICATION Refractory lined vessel and method of use This invention relates to refractory lined vessel, particularly a chlorinator, and its method of use.
During use of a chlorinator for chlorination of a titaniferous material existing refractory materials exhibit wear when used as linings and this necessitates expensive repair or replacement at frequent intervals. There is a need for such chlorinators having longer lives than at present between repairs.
According to the present invention a vessel suitable for use in the chlorination of a titaniferous material comprises an outer shell-like retaining wall having a closed upper end and a base, inlet means to introduce a titaniferous material into the vessel and outlet means located at or adjacent the upper end for the discharge of gaseous reaction products, said base having means to introduce a gas into the vessel and to distribute said gas over the horizontal cross-sectional area of the vessel, said retaining wall having a refractory lining and said base having refractory infill material between individual means to introduce and to distribute said gas and, said individual means, said lining and/or said infill material being formed of a refractory concrete containing an aggregate and a high alumina containing cementitious binder containing up to 20% by weight of added calcium chloride base on the weight of said refractory concrete.
Preferably the cementitious binder contains aluminium values in an amount of at least 50% by weight when expressed as AL2O3 and most preferably contains aluminium values in an amount of at least 65% of weight when expressed as Awl203 of the weight of the binder. The remainder of the composition of the binder will usually be constituted by a majority percentage by weight of calcium values and minor amounts of silica values and iron values together with other elemental values in trace quantities. Depending on the particular amount of aluminium values the amount of calcium values will be from 25% to 40% by weight when expressed as CaO of the weight of the binder.
Overall it is desired that the particular concrete formed on mixing the aggregate and binder usually will have a composition so that it contains aluminium values in an amount of 44% to 50% by weight expressed as AL2O3, silicon values in an amount of from 40% to 45% by weight when expressed as SiO2, iron values in an amount of not more than 2% by weight when expressed as Fe2O3 and calcium values in an amount of from 4% to 7% by weight when expressed as CaO.
The addition of calcium chloride to the mixture of aggregate and binder has been found to increase the life of refractory concrete by a surprising extent. This is most surprising particularly when considering the destructive atmosphere present in a chlorinator with the presence of chlorine gas, acid reaction products together with some inevitable oxychlorides. A simple addition of calcium chloride would hitherto hardly have been considered to be of value.
Nevertheless this addition is of considerable significance. The amount of added calcium chloride is up to 20% by weight of the refractory concrete dry mixture and preferably is from 1.5% to 10% by weight.
The chloride can be added in the dry form to the other ingredients or alternatively the chloride can be added as a solution in the water required to effect setting of the refractory concrete.
The proportion of aggregate to binder is chosen to produce the required composition of the final concrete but usually depending on the particular composition of the ingredients from 2.5 to 5 parts by weight of aggregate will be mixed with one part by weight of the binder. The most preferred proportion of aggregate to binder is 3 parts by weight of aggregate to one part by weight of binder.
The aggregate can have a wide range of particle size but usually will have a particle size range of 8 mm to dust. A typical useful aggregate is a fired flint clay of the desired size.
Sufficient water is added to the dry mixture to give the required consistency and to be sufficient to permit complete setting of the refractory concrete to take place. The mixture can be applied by casting, gunning, trowelling or by extrusion as is appropriate.
The vessel is of particular use in the chlorination of a titaniferous material to produce titanium tetrachloride. The chlorination is carried out in the presence of a carbonaceous reducing agent, e.g. coke, by chlorine gas passing upwardly through a bed of the reactants at such a rate and density as to maintain the bed in fluid suspension.
Normally the bed of material is heated to at least 8000C to initiate the chlorination reaction.
The bed of titaniferous material, which most suitably is ilmenite or more preferably mineral rutile, is retained within the chlorinator on the base formed by an array of gas distribution tubes or tuyeres carried by a lower support plate.
Refractory infilling material is provided between the gas distribution tubes. The gas distribution tubes or tuyeres can be formed of a refractory material similar to that used to form the lining.
Normally a wind box or gas distribution chest is located below the array of gas distribution tubes so that as to fluidise the bed and to effect the chlorination reaction can be fed to the tubes from a suitably located inlet.
One form of chlorinator constructed in accordance with the invention will now be described by way of example only with reference to the attached drawing which is a diagrammatic section of a suitable vessel.
The chlorinator consists of an outer shell 1 having a refractory lining 2. The upper end of the shell 1 is closed by a lined lid 3 and the shell 1 has an upper outlet 4 for chlorination products.
Across the base of the shell 1 is positioned an array or an assembly of gas distribution tubes 5 carried on a support plate 6 with the spaces between adjacent tubes 5 being fiiled by refractory infill 7 similar to that forming the lining 2. Below the support plate 6 is a wind box or gas distribution chest 8 having an inlet 9 for a gas.
In use the bed 10 of the titaniferous material to be chlorinated is carried by the array of tubes 5 and an inlet port 11 if provided through which the bed may be replenished in use.
The invention also includes a method of chlorination of a titaniferous material to produce titanium tetrachloride which comprises establishing a bed of a titaniferous material to be chlorinated and a reducing agent on the base of a vessel in accordance with the invention and heating the bed to the desired reaction temperature and passing chlorine gas through the gas distribution tubes to react with the titaniferous material and to maintain the bed in fluid suspension and collecting the titanium tetrachloride produced by the chlorination.
The invention is additionally illustrated in the following Example.
Example A chlorinator vessel having a base with an infill which had been cast from a concrete mixture containing a prefired flint clay aggregate and cementitious binder containing a source of alumina in an amount of 71% by weight expressed as Al203 on weight of binder, iron oxide in an amount of 0.25% by weight and a source of calcium in an amount of 27% by weight expressed as CaO was assembled. Calcium chloride was mixed with the water for setting and added to the dry mixture. The amount of calcium chloride was 2.5% by weight of the dry mixture. A bed comprising a mixture of coke and mineral rutile was formed on the base and heated to the temperature of chlorination.Chlorine gas was then passed through the bed for a period of 1200 hours during which time further supplies of the bed material was added and the chlorination products continuously withdrawn through an upper part of the vessel.
After 50 days continuous operation chlorination was ceased and the interior of the vessel examined after it had been allowed to cool.
Close examination of the base indicated that little or no erosion had taken place of the surface of the lining and in fact the tuyeres which had been cast from a conventional type of concrete mixture had eroded to leave the lining standing proud of the upper surface.
A similar infill material without added CaCI2 when used for a similar period had worn to such an extent that the tuyeres themselves stood proud of the surface of the infill.
It was estimated that the life of the infill containing CaCI2 was at least twice that of an infill free of added Cacti2.

Claims (12)

Claims
1. A vessel suitable for use in the chlorination of titaniferous material which comprises an outer shell-like retaining wall having a closed upper end and a base, inlet means to introduce a titaniferous material into the vessel and outlet means located at or adjacent to the upper end for the discharge of gaseous reaction products, said base having means to introduce a gas into the vessel and to distribute said gas over the horizontal cross-sectional area of the vessel, said retaining wail having a refractory lining and said base having refractory infill material between individual means to introduce and to distribute said gas and, said individual means, said lining and/or said infill material being formed of a refractory concrete containing aggregates and a high alumina containing cementitious binder having up to 20% by weight added calcium chloride based on the weight of said refractory concrete.
2. A vessel according to claim 1 in which the cementitious binder contains aluminium values in an amount of at least 50% by weight expressed as Al2O3 of the weight of the binder.
3. A vessel according to claim 1 or 2 in which the cementitious binder contains aluminium values in an amount of at least 65% by weight expressed as Al2O3 of the weight of the binder.
4. A vessel according to any one of the preceding claims in which the amount of calcium values is from 25% to 40% by weight expressed as CaO of the weight of the binder
5. A vessel according to any one of the preceding claims in which the particular concrete forming said lining and/or said infill contains aluminium values in an amount of from 44% to 50% by weight expressed as Al203, silicon values in an amount of from 40 to 45% by weight expressed as SiO2, iron values in an amount of not more than 2% by weight when expressed as Fe2O3 and calcium values in an amount of from 4% to 7% by weight when expressed as CaO
6. A vessel according to any one of the preceding claims in which the amount of calcium chloride is from 1.5% to 10% by weight on the weight of refractory concrete dry mixture.
7. A vessel according to any one of the preceding claims in which the amount of aggregate is from 2.5 to 5 parts by weight per 1 part by weight of binder.
8. A vessel according to claim 7 in which the amount of aggregate is 3 parts by weight to 1 part by weight of the binder.
9. A vessel according to any one of the preceding claims in which the aggregate has a particle size of 8 mm to dust.
10. A vessel according to any one of the preceding claims in which the aggregate is a fired flint clay.
11. A method of chlorination of titaniferous material which comprises establishing a bed of titaniferous material to be chlorinated and a reducing agent on the base of a vessel constructed in accordance with any one of the preceding claims and heating the bed to the desired reaction temperature and passing chlorine gas through the gas distribution tubes to react with the titaniferous material and to maintain the bed in fluid suspension and collecting the titanium tetrachloride thus produced by the chlorination process.
12. A method according to claim 11 in which the bed of titaniferous material is heated to at least 8000C to initiate the chlorination reaction.
1 3. A vessel suitable for use in the chlorination of a titaniferous material constructed and arranged substantiaily as described herein and shown in the accompanying drawing.
GB08235054A 1982-02-25 1982-12-08 Refractory lined vessel and method of use Expired GB2115802B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8205551 1982-02-25

Publications (2)

Publication Number Publication Date
GB2115802A true GB2115802A (en) 1983-09-14
GB2115802B GB2115802B (en) 1984-12-12

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ID=10528601

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GB08235054A Expired GB2115802B (en) 1982-02-25 1982-12-08 Refractory lined vessel and method of use

Country Status (8)

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JP (1) JPS58156535A (en)
AU (1) AU9168382A (en)
DE (1) DE3303099A1 (en)
ES (1) ES8406382A1 (en)
FR (1) FR2521870A1 (en)
GB (1) GB2115802B (en)
IT (1) IT1164869B (en)
ZA (1) ZA829416B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61141946A (en) * 1984-12-15 1986-06-28 望月精密機械工業有限会社 Cutter
US20070178028A1 (en) * 2004-02-23 2007-08-02 Eiichi Fukasawa Apparatus for production of metal chloride
JP5852604B2 (en) * 2013-04-22 2016-02-03 株式会社大阪チタニウムテクノロジーズ Dispersion disk and fluidized chlorination furnace equipped with the same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1396261A (en) * 1964-05-27 1965-04-16 Casting mass imitating marble
GB1292442A (en) * 1968-10-18 1972-10-11 Laporte Industries Ltd Improvements in and relating to fluidised bed reactors
PL81589B1 (en) * 1971-04-28 1975-08-30
CA1071245A (en) * 1976-01-15 1980-02-05 Dresser Industries Method of in situ fabrication of a monolithic refractory lining
DK242177A (en) * 1976-08-20 1978-02-21 Tashk Nachonoisslodovatelsky RAW MIXTURE FOR THE PRODUCTION OF FURNISHED CEMENT WITH HIGH ALUMINUM
FR2460892A1 (en) * 1979-07-12 1981-01-30 Inst Titana Titanium tetra:chloride prodn. - from granulated raw material, by chlorination in fluidised bed of carboniferous material

Also Published As

Publication number Publication date
DE3303099A1 (en) 1983-09-01
ZA829416B (en) 1983-09-28
ES518986A0 (en) 1984-07-01
FR2521870A1 (en) 1983-08-26
AU9168382A (en) 1983-09-01
JPS58156535A (en) 1983-09-17
IT1164869B (en) 1987-04-15
GB2115802B (en) 1984-12-12
ES8406382A1 (en) 1984-07-01
IT8347693A0 (en) 1983-02-10

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PCNP Patent ceased through non-payment of renewal fee