CN103037954B - Sequestration of carbon dioxide using tricalcium aluminate - Google Patents

Sequestration of carbon dioxide using tricalcium aluminate Download PDF

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CN103037954B
CN103037954B CN201180022310.8A CN201180022310A CN103037954B CN 103037954 B CN103037954 B CN 103037954B CN 201180022310 A CN201180022310 A CN 201180022310A CN 103037954 B CN103037954 B CN 103037954B
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carbon dioxide
stream
dioxide fixation
aluminate
solution
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CN103037954A (en
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史蒂文·菲利普·罗森贝格
埃里克·安托瓦妮特·约瑟夫·玛丽·博姆
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Texas 32 Woessner Aluminum Co. Ltd.
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BHP BILLITON WORSLEY ALUMINA PTY Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
    • 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
    • B01D53/80—Semi-solid phase processes, i.e. by using slurries
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
    • C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
    • C01F7/142—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent with carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/30—Alkali metal compounds
    • B01D2251/304—Alkali metal compounds of sodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/60—Inorganic bases or salts
    • B01D2251/604—Hydroxides
    • 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
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

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Abstract

A carbon dioxide sequestration process is disclosed. The process comprises the steps of a) introducing a source of carbon dioxide to a caustic aluminate solution to form a first treated stream comprising carbonate ions in solution and aluminium hydroxide in solid form; b) subjecting the first treated stream to solid/liquid separation to recover alumina values in the form of aluminium hydroxide and produce a first clarified treated stream; c) mixing the first clarified treated stream with tricalcium aluminate to form a second treated stream comprising calcium carbonate in solid form, aluminate ions in solution, and hydroxyl ions in solution; and, d) subjecting the second treated stream to solid/liquid separation to remove calcium carbonate within which carbon dioxide has been sequestered, and produce a second clarified treated liquor stream.

Description

Use tricalcium aluminate stabilizing carbon dioxide
Technical field
The present invention relates to fixing (sequestration) method of carbon dioxide.Especially, but the present invention relates to not only for the fixing means of carbon dioxide, to reduce the greenhouse gas emission of alumina refinery.
Background technology
In upper a century, Bayer process is for reclaiming oxidation aluminum values from bauxitic ore.The core of the method is following reversible equation, for gibbsite and boehmite or diaspore ore, is respectively (1):
Figure 1 illustrates the schematic flow diagram of the basic embodiment showing traditional Bayer process.First a part for mixed bauxite and the waste liquid of recirculation mixes, and stands grinding to reduce granularity.Then the soluble silica mineral that the slurry that the PROCESS FOR TREATMENT being " desiliconization " or " holding slurry (slurry holding) " via known (title) generates is present in bauxite with removal, typically with the form of insoluble sodium silicoaluminate.
Then the slurry of desiliconization and remaining waste liquid mix, via being called that the technique of " digestion (digestion) " extracts the oxidation aluminum values of bauxite.In digestion, manipulation condition is to advance equation (1) or (2) towards right-hand side.Between the period of digestion, in free caustic fusion bauxite, aluminiferous mineral are to form concentrated sodium aluminate solution, be left behind body refuse and the impurity of non-dissolution of minerals, it is passive iron oxide, hydroxide, (oxidation) hydroxide, titanium oxide and silicon-containing compound mainly.Usually owing to there is iron mineral, body refuse appearance is red, is thus commonly referred to " red soil ".By using the condition of high temperature and high pressure to promote digestion, and these so that depend on the ore type of process.The balance that equation (1) and (2) represent also can be moved to right-hand side by the concentration improving free caustic alkali (hydroxide ion).
After flash cooled, in the technique being called " clarification ", mother liquor is separated with body refuse.By slurry feed in one or more sedimentation basin, wherein solid particles sediment is removed, typically via being pumped to mud wash cycle to bottom.Assist being separated of mud and concentrate with flocculant, " former (the green) " liquid (or mother liquor) simultaneously only containing the meticulousst suspended solid overflows mud-settling pit.
Then usually typically pressure filter is used, by filtering the liquid that clarification is further separated out.The step that it is called " filtering (polishing) " filters is guaranteeing that during mother liquor is not containing the mud in suspension particle causing product alumina to pollute in addition be crucial.Independently, the cloth adopted in these filters blocks as quick as thought.Occur this is because the meticulous suspended solid in settling vessel overflow is absorbed in the knitmesh of filter cloth, then continue on the surface of filter to form dense resistive formation.
In order to prevent this problem, usually with " filter aid " to filtering filter supply feed, the effect of this filter aid prevents from being formed continuously the Solid Bed that mud particle is absorbed in block filter cloth, also makes liquid pass through the backlash freedom flowing of bed simultaneously.Desirable filter aid by be cheap, chemically inert, size be its mud particle can be made to be absorbed in and not confined liquid flowing or promote the blocking of filter cloth self.In most alumina refinery, this effect is undertaken by tricalcium aluminate (also referred to as TCA, C3A or C3AH6).
Mud wash cycle depends on counter-current decantation technique to reclaim the sodium aluminate re-used as far as possible, to make the minimization of loss of aluminium oxide and causticity base number, and purifies body refuse so that its mode can allowed with environment is discarded.Make the washer overflow of flowing out first paragraph mud kitchen sink subsequently flow into sedimentation basin, or mix with settling vessel spillage the mother liquor forming clarification.Typically, by the final stage of mud wash cycle, the body refuse of washing is evacuated to mud emission pond.Adverse current mud wash cycle washings, the recirculated water (being called " Chi Shui (lakewater) ") typically in fresh water, condensate liquid (condensed steam) or mud emission pond or above-mentioned combination supply.
Before delivering to precipitating phase, the clarified mother liquor of spilling sedimentation basin is made to stand filtration described above.In precipitating phase, the balance of equation (1) (again copying hereinafter) is impelled to move towards left-hand side to form pure Al (OH) 3, also referred to as " gibbsite ".
Via the gibbsite of hydrocyclone, thickener or filter precipitation and separation.Remaining liquid, evaporation is called " waste liquid (used liquid) " after removing excessive water, these excessive waters enter in technique along with bauxite and various washing step, and will containing aluminate ion and hydroxide ion, the amount of existence depends on temperature, the surface area of crystal seed (seed) and the time of staying of precipitating phase.Precipitation is promoted, as the concentration or the dilute solution that reduce temperature, add gibbsite crystal seed, improve aluminate ion by the oversaturated condition of increase liquid.In order to reclaim oxidation aluminum values and caustic alkali, recirculation waste liquid is with digestion.Thus the aluminium oxide containing dissolving through recirculation with the waste liquid of digestion is present in wherein.
According to the gibbsite crystallization classification that large young pathbreaker is formed during precipitating, fire product level material in rotary kiln or fluidized bed calcination stove, the particle of undersize is used as " crystal seed " simultaneously, and it contributes to the precipitation in the diaspore crystallization of precipitate phase period three.Firing period, gibbsite dehydroxylation is to form aluminium oxide.Meanwhile, the carbon dioxide of generation is the accessory substance of the combustion of fossil fuel for running calcining furnace.Also in flue gas, discharge carbon dioxide, these flue gases produce with the power station powered to alumina refinery by running, and also can be produced by limekiln in some alumina refinery.At this moment waiting, there is restriction in the option that can be used for affecting the discharge of firing the greenhouse gases that period produces.
The main target of Bayer process is from being supplied to solution to extract the oxidation aluminum values (Al) of maximum the bauxite of digestion economically, then reclaiming these aluminium oxide dissolved completely with the form precipitating period three diaspore from solution.The upper limit of refinery's precipitation productive rate (output) be by digestion temperature in particular liquid aluminium oxide solubility and at the temperature for precipitating in liquid aluminium oxide solubility between difference determine.Then thus conclude, the main target of most of alumina refinery is that this species diversity is maximized.
In alumina refinery, a main path of alumina loss to be evacuated to from sedimentation basin with body refuse in the liquid in mud wash cycle.The liquid of this oversaturated mother liquor has the aluminate ion with the mother liquor same concentrations delivering to precipitation effectively.The liquid overflowed in each stage of adverse current mud wash cycle becomes more dilution with more ice-cold gradually with washings.This improves the supersaturation of liquid effectively, promotes the precipitation of the gibbsite according to equation (1).Mud particle in residue has high surface area, and it promotes this precipitation of gibbsite in mud wash cycle further.Have lost any aluminium oxide precipitated by this way in mud wash cycle, as the aluminium oxide of dissolving any in the liquid delivering to mud emission pond.
Another approach of alumina loss is that aluminium oxide is integrated with in TCA filter aid, uses this TCA filter aid to remove the fine solid suspended during clarifying.Along with the past of time, TCA filter aid was easily polluted by the external foreign matters and became " useless (using) ".TCA is relatively inexpensive and easily produces.Under suitable condition, the calcium with the Suitable sources from such as white lime is reacted to form thermodynamically stable and sl. sol. TCA by caustic aluminate solution.The most often use this reaction to produce the TCA crystal of Control granularity in aluminum oxide industry, to be used as filter aid.In a lot of alumina refinery, useless (with what cross) TCA filter aid is pumped down to red soil treatment region, and can means annual 40 to 90 for typical refinery, the loss of the oxidation aluminum values of 000 ton of (quantity) level.By this way, useless filter aid means that alumina refinery stores or discarded weight most " solid basicity " usually.
Still the greenhouse gas emission reducing alumina refinery generation is needed.
Summary of the invention
According to a first aspect of the invention, provide a kind of carbon dioxide fixation (sequestration) method, the method includes the steps of:
A) in caustic aluminate (caustic aluminate) solution, introduce carbon dioxide source flow with the first process forming the carbanion that comprises in solution and aluminium hydroxide in solid form;
B) make first of step a) the process flow through by solid/liquid separation to reclaim the oxidation aluminum values of aluminium hydroxide form, and produce the first clarifying treatment stream;
C) the first clarifying treatment stream of step b) and tricalcium aluminate are mixed to be formed second of the calcium carbonate, the aluminate ion in solution and the hydroxide ion in solution that comprise solid form to process and flow; And
D) make second of step c) the process flow through by solid/liquid separation to remove wherein the calcium carbonate of stabilizing carbon dioxide, and produce the second clarifying treatment liquid stream.
In one form, at the temperature being not less than 50 ° of C, step c) is carried out.In another form, be not less than 50 ° of C and carrying out step c) at the temperature of the atmospheric boil do not flowed higher than the first process.In one form, heating steps b) the first clarifying treatment stream to carry out step c) at 50 ° of C and not higher than the temperature in the scope of atmospheric boil.
Preferably, caustic aluminate solution is Bayer liquor.In one form, Bayer liquor is one or more: useless Bayer liquor, the overflow stream of mud washing section or pond current.
In one form, the position that the method is included in digester (digester) downstream and settling vessel upstream further makes the second clarifying treatment stream of step d) be back to the step of alumina refinery.In one form, caustic aluminate solution has ' S ' concentration of 20 to 100g/L.In one form, the tricalcium aluminate used in step c) is TCA filter aid or useless TCA filter aid.
According to a second aspect of the invention, with reference to drawings and Examples, and as illustrated, provide basic carbon dioxide fixation method as described in this article wherein.
Accompanying drawing explanation
For the ease of understanding feature of the present invention in more detail, only by way of example, with reference to accompanying drawing, will several embodiments of method and apparatus be described in detail now, wherein:
Fig. 1 is the simplification conceptual flow chart of the basic embodiment of traditional prior art Bayer process;
Fig. 2 is the simplification conceptual flow chart illustrated for reclaiming the embodiment according to carbon dioxide fixation method of the present invention;
Fig. 3 illustrates for RWB and AC two campaign, the C/S comparative result in time of embodiment 1;
Fig. 4 illustrates the result of the matrix test program of embodiment 2, shows under constant ' S ' of 17.9g/L, final ' C ' under 30 ° of C, 60 ° of C and 95 ° C;
Fig. 5 shows the result of the matrix test program of embodiment 2, shows under constant ' S ' of 37.1g/L, final ' C ' under 30 ° of C, 60 ° of C and 95 ° C;
Fig. 6 illustrates the result of the matrix test program of embodiment 2, shows under constant ' S ' of 56.5g/L, final ' C ' under 30 ° of C, 60 ° of C and 95 ° C;
Fig. 7 illustrates the result of the matrix test program of embodiment 2, shows under constant ' S ' of 81.4g/L, final ' C ' under 30 ° of C, 60 ° of C and 95 ° C; And
Fig. 8 illustrates the result of the matrix test program of embodiment 2, shows under constant ' S ' of 100.7g/L, final ' C ' under 30 ° of C, 60 ° of C and 95 ° C.
Detailed description of the invention
Whole description employs normally used various term in aluminum oxide industry.In order to clear, these terms of definition now.
The term " liquid " that whole description uses refers to and comprises aluminate (Al (OH) 4 -) ion and hydroxyl or " causticity " (OH -) any solution of ion.In Bayer liquor, main component is sodium aluminate (NaAl (OH) 4) and NaOH (NaOH).
' A ' refers to the alumina concentration of liquid, and more particularly the concentration of sodium aluminate in liquid, is expressed as equivalent aluminium oxide (Al 2o 3) g/L.
' C ' refers to the caustic sodium concentration of liquid, and it is sodium aluminate and the sodium hydrate content sum of liquid, is expressed as the g/L concentration of equivalent sodium carbonate.
Thus ' A/C ' is alumina concentration and the ratio of caustic sodium concentration.
" free caustic alkali " is that C-A(caustic sodium concentration deducts alumina concentration), C and A is expressed as the g/L concentration of equivalent sodium carbonate separately.
Any liquid stream after term " waste liquid (liquid with crossing) " refers to gibbsite precipitating phase and before digestion.Typically waste liquid has low A/C ratio.Liquid after term " stoste " or " mother liquor " refer to digestion and before precipitation.Typically mother liquor has high A/C ratio.
" Chi Shui " be with collect rainwater be mixed in together with the supernatant liquid stream being back to refinery from mud emission pond (if use).Typically pond glassware for drinking water has the minimum A of any liquid stream.Due to the reaction of the carbon dioxide in Chi Shui and air, typically pond glassware for drinking water has high carbonate concentration.
" S " refers to alkali concn, or more particularly " C " and actual concentration of sodium carbonate sum, and again, this adds and is expressed as the g/L concentration of equivalent sodium carbonate.Therefore, S-C(alkali concn deducts caustic sodium concentration) give in liquid with the actual concentrations (Na of the sodium carbonate of g/L 2cO 3).
The carbonate impurities level of Bayer liquor is with the ratio of caustic alkali with sodium carbonate, or ' C/S ' represents.(not carbonato) bayer process liquor of complete causticization will have the C/S ratio of 1.00.
The term " aluminium hydroxide " used in whole description refers to the crystallization shape or amorphous compound that are made up of aluminium ion and hydroxide ion.An example of ' aluminium hydroxide ' is ' gibbsite ', and it is for having general formula Al (OH) 3three aluminium hydroxides.Sometimes gibbsite also means " hydrate " or " hibbsite " or three aluminium hydroxides in the literature ", the chemical formula Al of mistake in sometimes 2o 33H 2o represents.Term ' aluminium hydroxide ' also broadly enough cover ' boehmite (boehmite) ', it is single aluminium hydroxide.
Term ' crystal seed ' refers to the particle that general size is less than the Product size of nominal.The function of crystal seed is two kinds.First, crystal seed promotes/strengthens the generation of gibbsite, and secondly, crystal seed promotes the growth compared with megacryst.
' calcite ' is calcium carbonate (CaCO 3).
' TCA ' is tricalcium aluminate Ca 3[Al (OH) 6] 2, in cement industry symbol, it also uses chemical formula 3CaOAl usually 2o 36H 2o, (TCA6) or C3AH6 write.In a lot of alumina refinery, TCA is obtainable as the accessory substance of causticization.When using factory's liquid to prepare TCA, it can comprise impurity by making the anionic impurity be present in factory's liquid be incorporated in lattice." synthesis TCA " is in pure sodium aluminate solution instead of the material that uses factory's liquid to produce, because of but pure tricalcium aluminate.
" useless filter aid " refers to the TCA being used as filter aid in alumina refinery, and it is based on periodically discarded filter aid at the end of the cycle of operation of pressure filtration.About this point, useless filter aid keeps the chemical formula of TCA, and may be polluted by meticulous red mud solids.
" TS " refers to the sodium salt sum in all solution, is expressed as the sodium carbonate equivalent concentration with g/L.
Term ' autoprecipitation ' is commonly referred to as the growth of aluminium hydroxide and the generation of not accelerating oxidation aluminium.
" causticization " is the normally used term of technical staff in Bayer process field, to describe the method, by the method by adding white lime and precipitating insoluble calcium carbonate, removes carbonate, and replace with hydroxide from Bayer liquor.As the term " causticization " used in whole description, broadly refer to and wherein from liquid, remove impurity anions and any method of replacing with hydroxide ion.
With reference to figure 2, the carbon dioxide fixation method (10) according to one embodiment of the present invention is described now.In this embodiment, in the first reactor (18) to introducing carbon dioxide source (12) in caustic aluminate solution (14) to form the first process stream (20) of the aluminium hydroxide comprising carbanion in solution and solid form.Any suitable method can be used, such as bubble systems, in the first reactor (18), introduce carbon dioxide source (12).Carbon dioxide source can be any purity.Suitable source comprises the carbon dioxide in ' flue gas ' being present in flue or produced by power station or calcining furnace or is present in the carbon dioxide in exhaust or " flue gas " that produced by limekiln.
Do not wishing to be bound by theory, according to following reaction, carbon dioxide and the NaOH be present in the Bayer liquor stream of dilution react to produce sodium carbonate:
Alternatively or in addition, under suitable pH condition, carbon dioxide can react to produce sodium acid carbonate with the NaOH be present in the Bayer liquor stream of dilution.Lower than under the pH of 10.5, the formation of sodium acid carbonate becomes remarkable, thus, operates being for the mode of operation making sodium carbonate have precedence over sodium acid carbonate precipitation under higher than the pH of 10.5.
According to following reaction, carbon dioxide also reacts with the sodium aluminate be present in the Bayer liquor of dilution and comprises sodium carbonate and gibbsite to produce.
Then in suitable the first solid/liquid separator (22), make the first process stream (20) stand solid/liquid separation to reclaim with the oxidation aluminum values of aluminium hydroxide (24) form, and produce the first clarifying treatment stream (26).Then can mix the first clarifying treatment stream (26) and tricalcium aluminate (32) source to be formed second of calcium carbonate, the aluminate ion in solution and the hydroxide ion in solution comprised in solid form to process and flow (36) in the second reactor (34).
When not wishing to be bound by theory, according to following reaction, TCA and the sodium carbonate be present in the first clarifying treatment liquid stream react to produce calcium carbonate (as solid), sodium aluminate (in solution) and NaOH (in solution):
Second process stream (36) is to remove calcium carbonate and producing the second clarifying treatment liquid stream.The second solid/liquid separator (38) is used to make the second process stream (36) stand solid/liquid separation to produce the second clarifying treatment stream (40) and the second efflux of solids (38), this second efflux of solids (38) the mainly wherein calcium carbonate of stabilizing carbon dioxide and any unreacted TCA.Strengthen the second clarifying treatment stream (40) with aluminate ion and hydroxide ion, it can be back to any suitable location in Bayer process, such as, to settling vessel or liquid filtering filter.Second efflux of solids (38) is with the stable solid form that can easily discard.By this way, the form that the greenhouse gases discharged to make alumina refinery can reduce, secures carbon dioxide.
Flow down at high temperature and lower ' S ', it is more favourable that TCA changes into calcite.As described in more detail in the examples below, along with ' S ' increases, the gross production rate of ' C ' improves, but conversion ratio reduces (as shown by C/S).
With reference to figure 2, the caustic aluminate solution (14) being supplied to the first reactor (18) can be Bayer liquor stream that is waste and old or dilution, such as, from the waste and old Bayer liquor stream of the Bayer liquor of mud wash cycle or another kind of dilution, there is the optimum performance that the liquid more diluted that ' S ' concentration is 20 to 100g/L obtains.
For the optimum that kinetics is relevant, the second reactor (34) operates at the temperature being not less than 50 ° of C.When operating the second reactor (34) at the temperature of atmospheric boil being greater than the first process stream (36), preferably the second reactor operates under not flowing the temperature of the atmospheric boil of (26) higher than the first process being not less than 50 ° of C.Be to be understood that by directly heat the second reactor or by one or two the first process stream (26) of indirect or TCA source (32) heating of the second reactor (34) can be carried out.As described in more detail in the examples below, in the sodium carbonate liquor of 100g/L synthesis, adding waste and old TCA filter aid at the temperature within the scope of 90 ° of C to 98 ° of C and causing the TCA of 83% and 78% to be converted into calcite.
Stirring condition in first and second reactors (being respectively 18 and 34) is not critical, although the inclusion of each of the first and second reactors should be preferably and suspend completely.Depend on the relative concentration of various streams and the conversion ratio of generation that add in correlative factor such as operating temperature, separately container, the residence time in the first and second reactors (being respectively 18 and 34) can be changed.Thus residence time can be no more than in the 4 little scopes up to being no more than 20 hours.
The caustic aluminate solution (14) being supplied to the first reactor (18) can be useless (using) Bayer liquor stream, such as, from the useless Bayer liquor stream of mud wash cycle or the Bayer liquor of other dilutions, there is the optimum performance that ' S ' concentration is the liquid more the diluted acquisition of 20 to 100g/L.
Second process stream (36) is to remove calcium carbonate and producing the second clarifying treatment liquid stream.Use the second solid/liquid separator (38) to make the second process stream (36) stand solid/liquid separation to produce the second clarifying treatment stream (40) and the second efflux of solids (38), this second efflux of solids (38) is calcium carbonate and any unreacted TCA mainly.Strengthen the second clarifying treatment stream (40) with aluminate ion and hydroxide ion, it can be back to any suitable location in Bayer process, such as, and settling vessel or liquid filtering filter.By this way by aluminium oxide value transmit to mother liquor, wherein can reclaim during precipitating these oxidation aluminum values.
First and second solid/liquid separator (being respectively 22 and 38) can be any suitable solid/liquid separator comprising one or more gravity settling basin, pressure filter, cyclone separator or sedimentator, but optimum performance uses simple filter to obtain.
Use TCA to make it possible to reclaim caustic alkali and oxidation aluminum values from mud wash cycle by this way, otherwise due to precipitation or with soluble form and the liquid waste being attended by mud, these caustic alkali and oxidation aluminum values can be lost.Can be sent back to digest and be recycled in technique by gibbsite solid potentially, fixing (sequester) discards the CO in calcite solid effectively simultaneously 2gas, reduces the discharge (prerequisite is that calcium carbonate is without undergoing firing with regeneration lime) of greenhouse gases.Also the waste disposal of useless (using) TCA filter aid is considerably reduced.
With reference to the key element of the Bayer process flow chart shown in figure 1, the indicative flowchart of the example of the embodiment of Fig. 2 is described now.In adverse current mud wash cycle (50), the alumina concentration from the washer overflow of the first mud washer (52) is very high, typically is in settling section the about half of the mother liquor overflowing sedimentation basin (54).Use counter-current decantation, body refuse is pumped to second washer (56) etc. from the first washer (52), to the n-th washer (60), and first new water or Chi Shui (62) are introduced into (n-th) washer (60) last in mud wash cycle (50), and be spilled over to (n-1)th washer (64) etc., until the first mud washer (52).In traditional Bayer process, in mud wash cycle due to precipitation, and with soluble form in the liquid being attended by mud to body refuse treatment region, have lost oxidation aluminum values.Washer spillage in all stages of mud wash cycle, as most liquid, is oversaturated for gibbsite.Along with each washing step successively, washing spillage becomes more dilution and more ice-cold gradually, causes aluminium oxide to lose owing to being deposited on mud particle.
In one embodiment of the invention, the caustic aluminate solution (14) being supplied to the first reactor (18) is the cleaning solution overflowed from the (n-1)th washer (64).The present invention is equally applicable to process multiple washer overflow stream, and it is respectively processed in one or corresponding multiple first reactor (18) naturally.Be to be understood that the washer spillage that can similarly use from any other mud washer, but, when washer spillage take from the 2 to the (n-1)th washer (being respectively 56 and 64) any one or each time, the recovery of oxidation aluminum values is full blast, when caustic aluminate stream (14) is the overflow from first in mud wash cycle (50) or final washer (being respectively 52 and 60), be worst.The overflow from the first washer (52) is used to be nonsensical, because be under any circumstance supplied to sedimentation basin from the spillage of the first washer.The alumina concentration flowing to the spillage of final (n-th) washer (60) is similar to Chi Shui usually, therefore too low and do not have actual benefit.In addition, remove aluminium oxide in this stage almost not act on as far as mud wash cycle (50) for preventing gibbsite from precipitating.
The advantage of various aspects of the present invention is further described and shows by following examples and experimental test results.These embodiments and experimental test results are that various possible embodiment is described, and should not be construed as and limit the present invention by any way.The person skilled in the art will easily understand the Bayer process not only having a kind of form, each alumina refinery must, according to factors, be the character of pending bauxite the most significantly, changes the specific process conditions used.Thus the restriction of the special value that do not describe by following examples of the present invention or the sedimentation basin of type, mud washer, escharotic, solid-liquid separator.
embodiment 1:TCA is converted into calcite
Produce the TCA of synthesis in the lab, and in rotary water bath (RWB) and autoclave and at the temperature of 60 ° of C, make the sodium carbonate (Na of itself and 60g/L 2cO 3) reaction, the degree of calcite is converted into the dynamics and TCA that compare reaction.
When using RWB to test, the syringe of 20mL is used to sample with the interval of 5,10,20,30,45,60,90,120,180,240,300 minutes, 24,30,48,54 hours.By these sample filterings, cooling, then use analyzing purity, to measure ' A ', ' C ' and ' S ' concentration.After 54 hours, from RWB, remove remaining mixture and filter.Collect filter liquor, XRD washs solid as before wet sample research in ice-cold DI water.
When using autoclave (AC) to test, in AC, add the 60g/LNa of 1000mL 2cO 3, then seal and balance to 60 ° of C.In AC, add the TCA of 73.09g synthesis, then reseal.So that RWB tests the identical time sampling provided above, terminate sampling 30 hours instead of 54 hours.Slurries also filter, wash and as study above by discharge AC.
Give result in figure 3, which show the test C/S comparison in time for RWB and AC two series.Result shows two serial test TCA and is substantially converted into calcite completely.
embodiment 2: matrix test
Matrix test is intended to the concentration ([Na proving reaction temperature and sodium carbonate in the second reactor 2cO 3]) effect.The result of these tests demonstrates for given [Na 2cO 3], TCA is converted into calcite is at relatively high temperatures more favourable.Further, at a constant temperature, along with initial [Na 2cO 3] increase of (i.e. [S]), material Na 2cO 3reaction improves, but C/S realizes reducing.
Matrix test program is given in following table 1.
Table 1: matrix test condition
Each solution of 300mL cumulative volume is added in the polypropylene vial of 500mL, and is added in water-bath at each temperature.Once these bottles balance, add TCA with each amount.Carry out sampling under each time and analyze ' A ', ' C ' and ' S ' concentration.
dynamic test:
Design motivation test is being shown under the intermediate point condition provided in [1] with assessment, and TCA is converted into the speed of calcite.Thus, the Na of 40g/L is used 2cO 3test with 60 ° of C.Sampled at 5,15,30,45,60,90,120,180 and 240 minutes and analyze ' A ', ' C ' and ' S ' concentration.In each test, TCA is added (80% of final ' C ' concentration) in the carbonate of the consumption of 80%.The result of dynamic test is shown in following table 2.Can find out and achieve about 50% of ' C ' always change in 5 minutes in the beginning of 4 h run.This shows that reaction rate is quickly.Expect that this speed increases with higher temperature and higher initial ' S '.
Table 2: dynamic test result
material:
The TCA slurry of 12L is collected from alumina refinery.To filter and with hot wash TCA slurry.Solid wet is stored in sealable bag.Get wet subsample and carry out X-ray diffraction (XRD).Another one's share of expenses for a joint undertaking sample dry and carry out x-ray fluorescence analysis (XRF).By preparing sodium carbonate liquor by the volumetric flask of known Standard entertion 1L.Analytical standard is to measure ' C ' and ' S ' concentration.
In Fig. 4 to 8, illustrate the result of matrix test program, these figures show that final ' C ' under constant ' S ' of three temperature.It is more favourable that result shows that at high temperature TCA is converted into calcite, and the gross production rate of ' C ' increases along with the increase of ' S ', but efficiency reduces (as shown by C/S).
In matrix test program, be successfully made the conversion of TCA to calcite, result shows that higher temperature and lower ' S ' are conducive to the generation of conversion reaction.Conversion yield display is higher with higher initial ' S ', but the efficiency as measured by C/S reduces along with higher initial ' S '.The dynamic test display conversion rate of carrying out in the sodium carbonate liquor of 40g/L and under 60 ° of C is fast, reaches final ' C ' of about 50% in 5 minutes.
embodiment 3: mixing effect
At [the Na of 60 ° of C and 40g/L 2cO 3] under repeat the test method that provides in embodiment 2 and stir (if there is) to the impact of kinetics to measure.Determine the test using vigorous agitation autoclave to carry out and be no faster than the equivalent test using rotary water bath.
Owing to describe in detail some embodiments of the present invention, therefore the technical staff of field of chemical engineering can make a lot of modification and change by understanding when not deviating from basic inventive concept.Think all these change and modification within the scope of the invention, essence of the present invention is determined by description above and the claim of enclosing.
To be expressly understood, although refer to many prior art publications in this article, this quote do not form admit in these documents arbitrary section formed this area, Australia or any other national in the part of general knowledge.In the explanation of invention with subsequently in description of the invention, except the implication due to representation language or necessity, outside linguistic context needs in addition, word " comprises " or such as " comprises " or the modification of " containing " uses with inclusive meaning, namely specifies there is described characteristic in various embodiment of the present invention instead of get rid of this existence or add further feature.

Claims (14)

1. a carbon dioxide fixation method, comprises the following steps:
A) in caustic aluminate solution, carbon dioxide source is introduced to form the first process stream of the aluminium hydroxide of carbanion and the solid form comprised in solution;
B) make step described first process a) flow through by solid/liquid separation to reclaim the oxidation aluminum values of aluminium hydroxide form, and produce the first clarifying treatment stream;
C) by step b) described first clarifying treatment stream and tricalcium aluminate mix to be formed second of calcium carbonate, the aluminate ion in solution and the hydroxide ion in solution comprising solid form and process and flow; And
D) make step c) described second process flow through by solid/liquid separation to remove the calcium carbonate of wherein stabilizing carbon dioxide, and produce the second clarifying treatment liquid stream.
2. carbon dioxide fixation method according to claim 1, wherein, step c) be carry out being not less than at the temperature of 50 DEG C.
3. carbon dioxide fixation method according to claim 1, wherein, step c) be not less than 50 DEG C and carrying out at the temperature of the atmospheric boil do not flowed higher than described first process.
4. carbon dioxide fixation method according to claim 1, wherein, heating steps b) described first clarifying treatment stream to carry out step c under 50 DEG C to the temperature in the scope of atmospheric boil).
5. according to carbon dioxide fixation method in any one of the preceding claims wherein, wherein, described caustic aluminate solution is Bayer liquor.
6. carbon dioxide fixation method according to claim 5, wherein, described Bayer liquor be selected from useless Bayer liquor, the overflow stream of mud washing section and pond current one or more.
7. carbon dioxide fixation method according to claim 1, the position being included in digester downstream and settling vessel upstream further makes steps d) described second clarifying treatment stream be back to the step of alumina refinery.
8. carbon dioxide fixation method according to claim 7, wherein, described caustic aluminate solution has ' S ' concentration of 20 to 100g/L.
9. carbon dioxide fixation method according to claim 1, wherein, for step c) described tricalcium aluminate be TCA filter aid.
10. carbon dioxide fixation method according to claim 1, wherein, for step c) described tricalcium aluminate be useless TCA filter aid.
11. carbon dioxide fixation methods according to claim 6, the position being included in digester downstream and settling vessel upstream further makes steps d) described second clarifying treatment stream be back to the step of alumina refinery.
12. carbon dioxide fixation methods according to claim 11, wherein, described caustic aluminate solution has ' S ' concentration of 20 to 100g/L.
13. carbon dioxide fixation methods according to claim 6, wherein, for step c) described tricalcium aluminate be TCA filter aid.
14. carbon dioxide fixation methods according to claim 6, wherein, for step c) described tricalcium aluminate be useless TCA filter aid.
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