CN101223293A - Processing of metal chloride solutions and method and apparatus for producing direct reduced iron - Google Patents

Processing of metal chloride solutions and method and apparatus for producing direct reduced iron Download PDF

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CN101223293A
CN101223293A CNA2006800257851A CN200680025785A CN101223293A CN 101223293 A CN101223293 A CN 101223293A CN A2006800257851 A CNA2006800257851 A CN A2006800257851A CN 200680025785 A CN200680025785 A CN 200680025785A CN 101223293 A CN101223293 A CN 101223293A
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oxide
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reduction reaction
acid
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约翰·大为·温特
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Austpac Resources NL
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    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/18—Reducing step-by-step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C01B7/035—Preparation of hydrogen chloride from chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B7/00—Halogens; Halogen acids
    • C01B7/01—Chlorine; Hydrogen chloride
    • C01B7/03—Preparation from chlorides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
    • C01G1/02—Oxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/04—Ferrous oxide [FeO]
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0033—In fluidised bed furnaces or apparatus containing a dispersion of the material
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0073—Selection or treatment of the reducing gases
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
    • C21B13/146—Multi-step reduction without melting
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B15/00—Other processes for the manufacture of iron from iron compounds
    • 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
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
    • C22B5/14—Dry methods smelting of sulfides or formation of mattes by gases fluidised material
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • 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
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/36—Regeneration of waste pickling liquors
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

A process and apparatus for regeneration of acid and metal from spent acid liquors includes the steps of, optionally, concentrating (110) the liquor to a concentrated liquor or solid, pyrohydrolysing (114) to regenerate the acid and form metal oxide pellets, and reducing the oxide to metal in a two stage reduction reactor (116, 118) using a partially combusted fuel as reducing agent. Also disclosed is a two-stage reduction process and reactor for production of direct reduced iron (DRI) from iron oxide ores or wastes, including a first stage (416) in which the oxide feed is contacted with a fuel and a sub-stoichiometric amount of an oxygen source to produce a lower oxidation state oxide, and a second stage (418) in which the lower oxidation stage oxide is contacted with off-gases from the first stage to produce iron metal.

Description

The processing of metal chloride solutions and the method and apparatus of direct-reduced iron
Technical field:
The present invention relates to a kind of processing metal chloride solutions, for example leach or the method and apparatus of the spent acid solution of metal pickling, and relate to the production method and the device of a kind of direct-reduced iron (DRI) from the metalliferous mineral acid system.
Background technology:
Several important industrial production flow processs are arranged, and its byproduct is a metal chloride solutions, and it exists with the form of spent acid solution, contains metal chloride in this waste acid liquor.
This metalloid muriate liquid comprises:
● the waste acid liquor (but being not limited to mineral) that the acid dissolving of mineral substance is caused, for example well-known ilmenite.In this case, this kind acid may be hydrochloric acid, but is not limited thereto.
● by acid treatment, perhaps pickling, the what is called " pickle solution " that the etching metal surface is produced when perhaps cleaning iron rust or oxide film.In this case, this kind acid may be hydrochloric acid, but is not limited thereto.
In first kind of above-mentioned situation, according to following common response formula, ilmenite, a kind of titanium ore is dipped in the hydrochloric acid and produces artificial rutile and to contain iron and other muriatic waste acid liquor, and this waste acid liquor also contains a spot of excessive hydrochloric acid.
FeO.TiO 2+2HCl→FeCl 2+TiO 2+H 2O
Dissolve in the oxide components in the ilmenite (except iron) of hydrochloric acid, also can similarly dissolve and form their muriates separately.Usually contain by the solution that such reaction generated and to be similar to the listed composition of following table:
The metal chloride lean solution canonical analysis that the acidleach of table 1 ilmenite produces
Composition Mass percent % Grams per liter
TiCl 4 0.08 1.14
FeCl 2 27.37 368.59
CrCl 3 0.03 0.44
MgCl 2 0.56 7.55
CaCl 2 0.26 3.56
MnCl 2 0.29 3.9
SiCl 4 0.02 0.21
VCl 5 0.11 1.52
AlCl 3 0.56 7.57
HCl 3.71 50.00
H 2O 67.00 902.46
Under second kind of situation, had the tectal product made from steel of oxide compound or iron rust and need carry out so-called " pickling " usually, be about to steel and from the hydrochloric acid soln of heat or other acid solutions, pass through, to remove oxide compound or iron rust tectum.Under the situation of using hydrochloric acid, the reaction that is taken place can be reduced to following form:
Fe 2O 3+Fe+6HCl→3FeCl 2+3H 2O
The already known processes flow process of this processing metal chloride solutions concentrates on the regeneration and the reduction of acid, is used for acidleach or pickling cyclic regeneration and uses.
The regeneration of this acid is finished by thermal hydrolysis usually, and metal chloride and water and oxygen react in this process, are reduced into acid, and generates byproduct---metal oxide.
For the situation of iron(ic) chloride, the principal reaction that takes place in pyrohydrolysis process can be expressed as following form:
2FeCl 2+2H 2O+1/2O 2→Fe 2O 3+4HCl
Can carry out thermal hydrolysis in 600 ℃ to 1200 ℃ temperature range, the temperature range that still is recommended in 850 ℃ to 950 ℃ is carried out.Liquefied gas is generally air.Adding enough fuel keeps temperature of reaction and controls oxygen potential energy.The waste gas that contains products of combustion and hydrochloric acid vapour is reduced into the hydrochloric acid composition after processed.
One of two kinds of well-known methods of main at present use are carried out thermal hydrolysis, that is:
● carry out in spray column, liquid is injected in the cavity, and reacts with the hot gas that is produced by liquid state or gaseous fuel burning.In this case, the metal oxide product is that form with fine powder exists.
● carry out in fluidized-bed reactor, liquid is injected in the fluidized-bed of metal oxide of previous generation, by injecting gaseous state, liquid state, solid fuel or their mixture high temperature is kept.In this kind equipment, the resistates of metal oxide is that 1 millimeter to 2 millimeters small particles form exists with diameter.
Further develop, as the example among International Patent Application PCT/AU93/00056 (WO93/16000), metal chloride solutions at first was the form that is evaporated into a kind of dried particles before being injected into the thermal hydrolysis reactor of fluid bed type.According to the conventional way of the thermal evaporation of from salts solution, carrying out water, that the type of vaporizer all is recommended as fluid bed type usually or rotation type.
The treatment process of WO93/16000 has superiority especially for the acid regeneration in the acid leaching process flow process, because it can generate the high density that can be used further in the leaching operation, super azeotropic acid solution.
Here quoted the content of WO93/16000.
Other well-known acid regeneration methods comprise keramchemie facture (roast method), and in this method, metal chloride liquid generates inferior azeotropic acid solution not having to carry out thermal hydrolysis under the situation of pre-concentration.
Summary of the invention:
Purpose of the present invention just provides one through method improved, viable commercial, and the device of carrying out this method.
In brief, the invention provides a kind of from the waste acid liquor that contains metal chloride the method for regenerating acid and metal, comprise the following steps: successively
● at random, solution concentration is become concentrated solution, perhaps concentrated solution is solidified into solid-state metal chloride;
● thermal hydrolysis solution, concentrated solution or solid metal muriate in reactor, thereby regenerating acid and form metal oxide; And
● metal oxide is reduced into metal.
Comparatively ideal situation is, metal is an iron, perhaps mainly is iron.
A kind of preferred form is, the reduction operation is carried out in a second-stage reduction reaction, in first step reduction reaction, by using a kind of unburnt fuel as reductive agent, generate a oxide compound than the suboxide state, in the reduction reaction of the second stage, will than the oxygenate conversion of suboxide state metal.
Comparatively ideal situation is, first step reduction reaction is carried out in an one-level fluid bed reduction reactor, and in this reactor, metal oxide contacts with fuel and the amount of oxygen that is lower than stoichiometric(al).
Perhaps, fuel has taken place to contact before first step reduction reaction with oxygen.
Equally comparatively ideal situation is, the waste gas of first step reduction reaction is used as the reductive agent of subordinate phase second stage reduction reaction.
In further preferred form, waste gas from second stage reduction reactor is oxidized, thereby in the flow process concentrate and hydrolyzing process provides energy, be that waste gas by the oxide particle metallization stage provides and make the required hot gas of metal chloride solutions evaporation.
In further form, the present invention comprises the following steps: for the processing of metal oxide charging provides a kind of method
● in first step reduction reaction, the reductive agent that contains fuel and be lower than the amount of oxygen of stoichiometric(al) is contacted with the metal oxide charging, thereby form oxide compound than the suboxide state; And
● oxide compound and waste gas than the suboxide state that first step reduction reaction is generated are supplied with second stage reduction reaction, thereby will be reduced into metal than the oxide compound of suboxide state.
Comparatively ideal situation is, the first step and second stage reduction reaction are all finished in the first step and second stage fluid bed reduction reaction chamber respectively.
Comparatively ideal situation is, the metal oxide charging is formed when carrying out thermal hydrolysis by the waste acid liquor that contains metal halide (preferably muriate).
Other aspects of the present invention provide in the claims.
Description of drawings:
Below by accompanying drawing embodiments of the invention are further described, accompanying drawing comprises:
Fig. 1 is the processing flow chart of the scrap metal chloride soln of first embodiment of the present invention.
Fig. 2 is the processing flow chart of the scrap metal chloride soln of second embodiment of the present invention.
Fig. 3 is the processing flow chart of the scrap metal chloride soln of the 3rd embodiment of the present invention.
Fig. 4 is the processing flow chart that becomes metallic iron from iron ore.
Embodiment:
Fig. 1 has illustrated first embodiment of the present invention, and it has comprised the thermal hydrolysis evaporation and the granulating of metal chloride (MeCl) solution before.
The waste acid liquor that iron or other metal oxide leachings are produced, perhaps the spent acid dilution that produced of steel or metallic surface precision work is sprayed on the vaporizer 110 of fluidized-bed, rotary kiln or other appropriate forms.Iron of separating out from vaporizer or metal chloride product at first are granular solids.For this vaporizer provides the hot gas of thermal source is the waste gas that comes from hereinafter described two metallization stages, and in the afterburner part 112 of vaporizer further oxidation takes place.
The product that comes out from vaporizer is sent to the thermal hydrolysis reactor 114, this reactor is the fluidized-bed form normally, in this reactor, iron or other metal chlorides react with water in 600 ℃ to 1200 ℃ temperature ranges that comparatively are fit to, and are converted into metal oxide.Used water may be provided by the burning of employed fuel and the remaining crystal water that comes from vaporizer in reactor in the reaction.
Concentrate, granulating, thermal hydrolysis operation and equipment thereof and operating parameter be commonly known, and detailed elaboration arranged in WO93/16000.
It should be noted that waste liquid or spissated waste liquid can be supplied to the thermal hydrolysis reactor by granulating material substitution partly or completely.
Metal oxide particle outputs to the fluidized bed gasification reactor 116 (gasifier) from the thermal hydrolysis reactor under the condition of high temperature, and this is as first step reduction reactor, and operating temperature is roughly 1000 ℃ ± 100 ℃.Can provide solid-state, liquid state or gasiform hydrocarbon fuel to gasifier, as long as meet local practical situation and cost structure.Suitable fuel can comprise coal, fuel oil or Sweet natural gas.
In gasifier, fuel is converted into the reducing gas that mainly contains hydrogen and carbon monoxide.
As further embodiment, can enlarge the kind of first step reducing apparatus charging, perhaps (discuss), substituting after a while as expanded skin and sediment fully by iron ore or metal oxide refuse with reference to figure 4.Perhaps, the metal oxide refuse can mix with metal chloride solutions before evaporization process mutually.
Related gasification reaction is very complicated, but has made big quantity research and report in the literature.Enumerate some below and comparatively simply react example:
C+O 2→CO 2
2C+O 2→2CO
2C+1 1/2O 2→CO+CO 2
2C+3H 2O→CO+CO 2+3H 2
CH 4+2O 2→CO 2+2H 2O
CH 4+H 2O→CO+3H 2
The required oxygen of these reactions comes from surrounding environment or preheating air feed, and can be oxygen enrichment or non-oxygen enrichment.Target is to guarantee enough oxygen, makes it have enough heat outputs to keep thermo-negative reaction, thereby is that simultaneous metal oxide reduction reaction generates necessary CO and H 2For example, only need 30% to 50% oxygen supply amount of stoichiometric(al) combustion requirements, just can obtain gratifying result.
The FeO bed is as the catalyzer of gasification reaction.
In gasifier, metal oxide as ferric oxide compound, is converted into suboxide rapidly, as ferrous iron, and can not metallize.Reduction is very important apace, can make it mainly generate FeO like this, and generates the Fe of intermidate oxide with minimizing 3O 4, because too high Fe 3O 4Per-cent will cause incipient fusion, and " viscosity " phenomenon of the non-fluidization of fluidized-bed occur.
The reaction that takes place in first step reduction is:
3Fe 2O 3+H 2→2Fe 3O 4+H 2O
3Fe 2O 3+CO→2Fe 3O 4+CO 2
Fe 3O 4+H 2→3FeO+H 2O
Fe 3O 4+CO→3FeO+CO 2
Be derived from gasifier, the solid oxide composition granule one of partial reduction mainly is that FeO-enters metallization fluidized-bed reactor 118 by pneumatic " J-valve " hydraulic efficiency installation or the lifting of other suitable device.Be used as liquid state medium the second stage or the metallization reaction device from first step reactor expellant gas, and contain the required remaining reducing gas H of enough reactions 2And CO.Coal is used as the fuel of first step reduction reaction, can generate charcoal in first step reaction, and is brought into together in the reaction of the second stage with oxide particle.The temperature of second stage chamber of the reactor is lower than the temperature in the first step reactor slightly, as is roughly 900 ℃ ± 100 ℃.In this reactor, be converted into metal to greatest extent from oxide compound, the chances are one hour for required time.
The reaction that takes place in the reduction of the second stage is:
FeO+CO→Fe+CO 2
FeO+H 2→Fe+H 2O
In the reduction reaction of the second stage, use waste gas, the Fe in the first step reactant from first step step of reaction 3O 4, its ratio is because react with CO, and minimizing gradually.
Fe 3O 4+CO→3FeO+CO 2
FeO+CO→Fe+CO 2
The resultant in metallization stage is to be indirectly cooled under the condition of vacuum, has so just avoided resultant that oxidation takes place when temperature raises.In accordance with regulations, with before air contacts, metallized particle must be cooled to below 200 ℃ or low temperature more.
Solid cooling device 120 may be more suitable in the present known technology indirectly.As shown in water cooler, air is as indirect heat-eliminating medium, and the warm air of generation is supplied with gasifier 116.
As mentioned above, being used for the hot gas of evaporated metal chloride soln, is that the waste gas in origin autoxidisable substance granular metal stage provides.At first by afterburner 112, carbon monoxide and hydrogen excessive in afterburner are converted to extra heat to gas, and these heats are used by vaporizer.And the heat that reclaims from the thermometal particle can be used for the air of pre-heat supply first step reduction reactor or factory's elsewhere.
Therefore, compare, be expected at the metallization operation, increased below 20% than required total fuel quantity with the technical process of WO93/16000, most of about 10%, but in fact, it has increased the economic worth of end product.
And above-mentioned technical process provides a solution for iron and steel industry, carries out the processing and the ferriferous oxide refuse of Acidwash solution, as the cyclic regeneration of expanded skin and sediment powder, produces regenerating acid and direct-reduced iron as value product.Can add the sediment powder of high zinc to waste liquid, and be limited in the passive iron oxide particle that the thermal hydrolysis operation produces, not have metalized.
Acid regeneration factory can also handle the waste water that is produced in the normal steelmaking process, or the on-the-spot rainwater that flows away.May contain trickle oxide compound, oil (from Steel Mill), coal dust/coal or muriate in these water, according to pollutant component, these water are fed to vaporizer or are used for acid and absorb.
Present method can not produce solid or Liquid wastes, and in the test process, the content of Dioxins and furans is lower than the content of examination criteria.
Service data
Ilmenite is carried out hydrochloric acid leaches, carry out small scale experiments, obtained time column data from the lean solution of its acquisition:
Supply to the solution of vaporizer.The solution composition that supplies to vaporizer is shown in above-mentioned table 1.
Evaporation stage.Muriatic evaporation of solid iron and drying have reached and experimental formula FeCl 2.1.5H 2Therefore the pairing so-called crystal water state of O will provide enough water to carry out the thermal hydrolysis reaction.
Thermal hydrolysis.The standard temperature of carrying out thermal hydrolysis is between 850 ℃ to 950 ℃.
Reduction.The iron oxide particle that is derived from thermal hydrolysis at first is reduced the unit price state, reverts to metallic state then fully.Related data is listed in following table 2.
The temperature of first step reaction is 950 ℃, and the hold-time is half an hour.
The temperature of second stage reaction is 930 ℃, and the residence time is two and one-half-hours.
Table 2 reduction is supplied with and the resultant analysis
Compound Unit Be derived from the oxide compound of thermal hydrolysis Metallization product
TiO 2 Mass percent % 0.11 0.16
Fe 2O 3 “ 95.5 0
FeO “ 6.0
Fe “ 0 89.7
Cr 2O 3 “ 0.06 0.08
MgO “ 0.84 1.18
CaO “ 0.02 0.03
MnO “ 1.64 2.29
SiO 2 “ 0.13 0.18
V 2O 5 “ 0.60 0.84
Al 2O 3 “ 0.38 0.54
P 2O 5 “ 0.004 0.005
Nb 2O 5 “ 0.002 0.003
The slag index Ratio Inapplicable 1.7
Sponge iron Mass percent % Inapplicable 1.6
The iron product that this experiment obtains is fire-retardant; Therefore need not carry out consolidated block or special processing to it at later safe handling.
Chemical ingredients and physical condition are considered to meet supplies with founding metal or STEELMAKING PRODUCTION, for example as the charging of electric arc furnace.
Operating pressure.Embodiments of the invention are worked under barometric point or in the low pressure environment basically, need not authenticate any groundwork container or equipment according to Australian national standard AS1210-1997 and amendment.
Fig. 2 has illustrated second embodiment of the present invention, and the scrap metal chloride soln among the figure directly supplies in the thermal hydrolysis reactor 214, and does not evaporate in advance and granulating.
In the embodiment of Fig. 2, require the more jumbo thermal hydrolysis reactor except supplying with solution owing to the metal chloride that will handle more dilutions, its working process and operation scheme all are similar to the description of above Fig. 1 of proximate composition parts.
In the arrangement of Fig. 2, the waste gas that reacts from second-stage reduction is fed in afterburner 212 and the waste heat recovery unit 213, and used heat is recovered the elsewhere that is used for factory.
In the arrangement of Fig. 3, directly supply to from the waste gas of second-stage reduction reaction 318 and further to burn in the thermal hydrolysis device 314 and reclaim heat.
In Fig. 2,3,4, Ref. No. is similar to the numbering among Fig. 1, uses " 200-series " numbering among Fig. 2, uses " 300-series " numbering among Fig. 3, uses " 400-series " numbering among Fig. 4.
Fig. 4 has illustrated another alternate embodiments, and here, powdered iron ore or ferriferous oxide waste material are reduced into iron.
Use is from residual chemicals in the waste gas of second-stage reduction reactor 418 and heat energy, and iron ore or ferriferous oxide powder are that 3 millimeters particle one is fed in the fluidized-bed preheater 422 just like diameter.Contain CO and H 2Waste gas be supplied in the afterburner 424 of preheater 422 bottoms, combustion gases supply in the fluidized-bed.
The aliment of preheating is fed into secondary in the same way in the reduction reactor 416,418, and its operation scheme is with reference to the description of above Fig. 1 to 3.
Though above the present invention is set forth by specific embodiments, but the present invention is not limited thereto, it can contain the attainable variation scheme of those skilled in the art in the prior art, and all changes scheme that is equal to the spirit and the scope of claim all will be capped.
In this manual, word " comprises " should be understood as that it is " broad sense ", promptly " comprises ", therefore is not limited to the scope of " narrow sense ", i.e. the meaning that " only comprises ".The several words that occur in this specification sheets " comprise " " being comprised " " comprising " all above same understanding.
Unless should be understood that and represent that opposite content, this paper quoted any document of prior art, and be not equal to admit this formerly technology in technical field related to the present invention, be well-known technology.

Claims (18)

1. the method for regenerating acid and metal from a waste acid liquor that contains metal chloride comprises the following steps: successively
A) at random, solution concentration is become concentrated solution, perhaps concentrated solution is solidified into solid-state metal chloride;
B) thermal hydrolysis solution, concentrated solution or solid metal muriate in reactor, thereby regenerating acid and form metal oxide; And;
C) metal oxide is reduced into metal.
2. according to claim 1 a kind of from the waste acid liquor that contains metal chloride the method for regenerating acid and metal, it is characterized in that metal is an iron, perhaps mainly be iron.
3. according to claim 1 a kind of from the waste acid liquor that contains metal chloride the method for regenerating acid and metal, the operation that it is characterized in that reducing is carried out in a secondary and reduction reaction.
4. according to claim 3 a kind of from the waste acid liquor that contains metal chloride the method for regenerating acid and metal, it is characterized in that in first step reduction reaction, by using a kind of unburnt hydrocarbon fuel, generate a oxide compound than the suboxide state as reductive agent.
5. according to claim 4 a kind of from the waste acid liquor that contains metal chloride the method for regenerating acid and metal, it is characterized in that first step reduction reaction carries out in an one-level fluid bed reduction reactor, in this reactor, metal oxide contacts with fuel and the amount of oxygen that is lower than stoichiometric(al).
6. according to claim 4 a kind of from the waste acid liquor that contains metal chloride the method for regenerating acid and metal, it is characterized in that described oxygen is supplied to described one-level reduction reaction.
7. according to claim 4 a kind of from the waste acid liquor that contains metal chloride the method for regenerating acid and metal, it is characterized in that the waste gas of first step reduction reaction is used as the reductive agent of subordinate phase second stage reduction reaction.
8. according to claim 3 a kind of from the waste acid liquor that contains metal chloride the method for regenerating acid and metal, it is characterized in that from the waste gas of second stage reduction reactor oxidized, thereby in the flow process concentrate and hydrolyzing process provides energy.
9. according to claim 1 a kind of from the waste acid liquor that contains metal chloride the method for regenerating acid and metal, it is characterized in that the waste gas from the oxide particle metallization stage is used to the evaporation of metal chloride solutions.
10. according to claim 2 a kind of from the waste acid liquor that contains metal chloride the method for regenerating acid and metal, further comprised the operation of adding ferriferous oxide to the metal chloride aqueous solution.
11. the method for a metal oxide treated comprises the following steps:
A) in first step reduction reaction, the reductive agent of the oxygen source amount that contains fuel and be lower than stoichiometric(al) is contacted with the metal oxide charging, thereby form oxide compound than the suboxide state; And
B) oxide compound and the waste gas than the suboxide state that first step reduction reaction are generated are supplied with second stage reduction reaction, thereby will be reduced into metal than the oxide compound of suboxide state.
12. the method for a kind of metal oxide treated according to claim 11 is characterized in that described metal is an iron.
13. the method for a kind of metal oxide treated according to claim 12 is characterized in that the oxide compound than the suboxide state mainly is FeO.
14. the method for a kind of metal oxide treated according to claim 10 is characterized in that the first step and second stage reduction reaction all finish respectively in the first step and second stage fluid bed reduction reaction chamber.
15. the method for a kind of metal oxide treated according to claim 14 comprises that the mode with inert gas flow is sent to second stage reaction chamber to the oxide compound than the suboxide state from first step reaction chamber.
16. the method for a kind of metal oxide treated according to claim 12 is characterized in that described metal oxide charging is a kind of iron ore.
17. the method for a kind of metal oxide treated according to claim 11 is characterized in that described metal oxide charging is granular metal oxide, it is formed when carrying out thermal hydrolysis regeneration by the waste acid liquor that contains metal halide.
18. the method for a kind of metal oxide treated according to claim 12 is characterized in that described metal halide is an iron(ic) chloride.
CNA2006800257851A 2005-06-15 2006-06-15 Processing of metal chloride solutions and method and apparatus for producing direct reduced iron Pending CN101223293A (en)

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