CN101306826B - Process for extracting metallurgy-level aluminum oxide from fly ash or slag - Google Patents
Process for extracting metallurgy-level aluminum oxide from fly ash or slag Download PDFInfo
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- CN101306826B CN101306826B CN200810115355XA CN200810115355A CN101306826B CN 101306826 B CN101306826 B CN 101306826B CN 200810115355X A CN200810115355X A CN 200810115355XA CN 200810115355 A CN200810115355 A CN 200810115355A CN 101306826 B CN101306826 B CN 101306826B
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Abstract
The invention relates to a method for comprehensive utilization of pulverized coal ash or furnace cinder, particularly to a method for extracting metallurgical alumina from pulverized coal ash or furnace cinder. The method comprises the steps of screening fine iron sands from the pulverized coal ash or furnace cinder, separating floating beads through floatation, pre-desiliconizing, producing white carbon black, producing alumina, and producing cement from waste residues. The inventive method improves the mass ratio of alumina and silicon oxide in an ore concentrate and the grade of pulverized coal ash or furnace cinder as a bauxite resource through optimization and modification of formula and process conditions in pre-desiliconizing of pulverized coal ash or furnace cinder and other processes, so as to provide a new route for extracting alumina form the pulverized coal ash or furnace cinder. At the same time, during the alumina extraction process, the method can be used for continuous and gradual extraction fine iron sand, floating beads and aluminum oxide as well as combined production of cement, so as to realize the comprehensive utilization of the pulverized coal ash or furnace cinder.
Description
[technical field]
The present invention relates to the resource utilization method of a kind of flyash or slag, relate in particular to a kind of method of from flyash or slag, extracting metallurgical-grade aluminum oxide.
[background technology]
From flyash or slag, extract aluminum oxide and be flyash or slag high value added utilization as a kind of secondary resource, than flyash or slag are applied to build, the research of construction and agriculture field, the research of extracting useful resources such as aluminum oxide from flyash or slag still is in theoretical research stage at present, and the technological line that can be used for suitability for industrialized production is very limited.The research that overseas utilization flyash or slag extract aluminum oxide or aluminium hydroxide starts to walk early, and as far back as the 1950's, the lattice day Mike of the Polish Krakow institute of mining and metallurgy teaches with high alumina coal gangue or aluminous fly-ash (Al
2O
3＞30%) is main raw material, adopts Wingdale calcination method, therefrom extract aluminum oxide and utilize its residue to produce silicate cement, obtained some achievements in research, and obtained two patents in Poland in nineteen sixty.
The report of external relevant this respect was less in the last few years, newer achievement in research is that employing alum mesosome methods such as Park have been extracted aluminum oxide (PARK H C from flyash, PARKY J, STEVRENSR.Synthesis of alumina from high purity alum derived from coal flyash.Materials science and Engineering, 2004,367:166-170, PARK HC, PARKY J, STEVRENS R etc., flyash extract high purity alum borolon, Materials Science and Engineering, 2004,367:166-170).
China extracts the research of aluminum oxide from flyash or slag can trace back to the 1950's equally, to 1980, metallurgical scientific research institution, Anhui and Hefei cement institute propose to extract aluminum oxide, its silico-calcium slag operational path as cement raw material with limestone sintering-yellow soda ash dissolving-out process from the powder ash, in February nineteen eighty-two by specially evaluation.Building materials research institute of Ningxia autonomous region has launched the research of alkali-lime sinter process extracting aluminum oxide from flyash before and after 90 years, one of its characteristics are exactly earlier flyash to be carried out adopting alkali-lime connection therefrom to extract aluminum oxide again after the desiliconization processing.Inner Mongol Meng Xi group, Inner Mongol University of Technology and Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences do, and have carried out the research in 10 years nearly, have obtained the technological line of cover limestone sintering method extraction oxygen aluminium and jointly producing cement at present.In addition, Northeastern University has also launched similar research in Shanxi, achieve initial success at present.
Extract method of alumina and can be divided into acid system, alkaline process and soda acid hybrid system from flyash by the acid-basicity of main additive, the relative merits of some common methods and the subject matter of existence are described below:
The more representational method of acid system is the sulfuric acid to leach method, and this method is: at first the NH4F with finite concentration and volume soaks flyash as solubility promoter, uses the H of finite concentration and volume then
2SO
4, under a constant temperature, dissolving, Al is with Al
2(SO
4)
3Form from flyash, leach, remove and add (NH behind the impurity F e
4)
2SO
4, reaction generates NH with it
4Al (SO
4)
212H
2O heats NH down at 950 ℃ at last
4Al (SO
4)
212H
2O just can obtain Al
2O
3
Comparatively going deep into comprehensive of alkaline process research, representative method is that limestone sintering method and soda-lime burn method.Five sixties of the limestone sintering genealogy of law, China introduced from USSR (Union of Soviet Socialist Republics), and this method also is to extract aluminum oxide method the most commonly used both at home and abroad from fine coal.
Hybrid system is exactly baking mixed with certain proportion and flyash with yellow soda ash earlier, uses dilute hydrochloric acid (or dilute sulphuric acid) to dissolve then, generates silica gel and AlCl
3[perhaps Al
2(SO
4)
3] solution, filtered through silica gel is used for further preparing white carbon black, filtrate is carried out adding after the removal of impurities NaOH neutralize, solution reaches the certain pH value postprecipitation and separates out Al (OH)
3, last calcination Al (OH)
3Obtain Al
2O
3
Above-mentioned several method respectively has advantage, the Al that acid system is produced
2O
3Purity is higher, and the one-tenth quantity of slag in the whole technological process is few; Alkali process is comparatively simple, relatively is suitable for scale operation; And the soda acid hybrid system is at the Al that flyash is surpassed 90%
2O
3When proposing, also most of silicon oxide is wherein extracted, the silicon oxide of proposition both can have been made silica gel, also can further prepare white carbon black.All there is certain shortcoming in aforesaid method: acid system has drawn NH
4F is as solubility promoter, and NH
4F is easy to the volatilization decomposition or generates fluorochemical with other substance reaction in being subjected to thermal process, fluorochemical has very big harm and contaminate environment to the people, and H
2SO
4A large amount of uses also make this scheme be difficult to industrialization; Limestone sintering method in the alkaline process causes energy consumption too high because the usage quantity of Wingdale is excessive, and becomes the quantity of slag excessive after the alumina extraction, is example with Meng Xi group, and 1 ton of aluminum oxide of every production approximately will produce 9 tons of slags.Main is that useful components such as the non-crystalline state silicon oxide in the flyash glassy phase all are not used appropriately, but directly enter in the slag.For above-mentioned reasons, this method of domestic usefulness is extracted Al
2O
3Producer almost all stop production; Handle though the soda-lime sintering process that building materials institutes in Ningxia adopts has carried out pre-desiliconization with NaOH solution to flyash in advance, therefore the one-tenth quantity of slag of 1 ton of aluminum oxide of every production just decreases than limestone-based process.But it only is 24.3% that this technology exists pre-desiliconization rate low, and, desiliconization liquid higher to the desiliconization equipment requirements prepares that desiliconization recycles the too high unfavorable factor of energy consumption with sodium hydroxide solution in the white carbon black process, so this method fails successfully to promote industrial equally; The strong acid of soda acid hybrid system, consumption is excessive, and AlCl for soda ash (perhaps caustic alkali)
3Impurity such as Fe, Ti is difficult to remove in the solution, and these all are the unfavorable factors that limits this technical scheme industrialization.
In sum, in recent years, most of achievement in research of extracting both at home and abroad useful resources such as aluminum oxide from flyash only has theory significance, the major cause that limits these achievement in research industrialization have following some:
1, not system is studied in the extraction of flyash useful resources, for example, some is research extraction aluminum oxide separately, and some specialize in the extraction silicon oxide, some special ferric oxide that extracts, some specialize in extraction carbon, and other are specialized in and extract trace element, and these researchs are all established one's own system, the extraction of resource is not carried out interrelated, integration, and make it to become a feasible overall plan, and make extraction cost high, be difficult to carry out Industry Promotion.
Even 2 extract the research of aluminum oxide or silicon oxide separately, obtained technological line is weighed from extraction yield, energy consumption, material consumption, environmental protection and operability, all there is certain defective, thereby limit its Industry Promotion, in China, also there is not the complete Ash Utilization of a cover system to utilize achievement in research so far.
[summary of the invention]
Given this, this patent proposes a kind of method, purpose is with flyash behind the fired coal combustion of fuel-burning power plant or slag, with its raw material sources as the aluminum oxide that extracts metallurgical grade, by improving the alumina silica ratio (mass ratio of aluminum oxide and silicon oxide) in the concentrate, promoted the taste of flyash or slag, extracted aluminum oxide for flyash or slag utilization and opened up new road as bauxite resource.
For achieving the above object, the invention provides a kind of from from flyash or slag, extracting the method for metallurgical-grade aluminum oxide, comprising following steps:
Steps A: slag is ground, stir behind the adding sodium hydroxide solution;
Step B:, get pre-desiliconization slurries with the pre-desiliconization of slurries;
Step C: solid-liquid separation and concentrate washing: pre-desiliconization slurries solid-liquid separation, liquid portion is pre-desiliconization filtrate, solid part is a filter cake, with hot water drip washing filter cake, with the filtrate collection behind the drip washing filter cake, merge the back pre-desiliconization dope that is together with the filtrate after pre-desiliconization slurries separate, continue to circulate with hot sodium hydroxide solution or hot water drip washing filter cake, filtrate after to the last the content of sodium oxide and silicon-dioxide roughly will wash after quite for the last time in the filtrate behind the once washing and the pre-desiliconization dope merges with pre-desiliconization dope, changing other hot sodium hydroxide solution or hot water again continues filter cake is washed, the mass percentage content of sodium oxide＜8.8% in filter cake, stop filter cake washing, through the oven dry of the filter cake after the washing, be concentrate, the alumina silica ratio of concentrate is 1.4: 1～1.6: 1;
Step D: with pre-desiliconization dope and with pre-desiliconization dope in the roughly suitable filter cake washing liquid of the content of sodium oxide and silicon-dioxide carry out obtaining being the white carbon black slurries after carbon branch, the ageing that collecting filtrate after the white carbon black slurries solid-liquid separation is pre-desiliconization mother liquor after merging; After pre-desiliconization mother liquor went causticization, solid filter cake was the causticization slag, and filtrate is pre-desiliconization circulating mother liquor, directly as pre-desiliconization sodium hydroxide solution;
Step e: with causticization slag and the yellow soda ash after concentrate, lime or the pre-desiliconization mother liquor causticization, dry grind, mixing is raw material, is grog behind the raw material sintering, grog and sodium carbonate solution carry out stripping; Carry out solid-liquid separation after the stripping, solid is a filter cake, and liquid is filtrate, and filtrate collection is a crude liquor of sodium aluminate, is that white clay is standby after the filter cake washing;
Step F: behind the deep desilication of crude liquor of sodium aluminate, carry out carbonating and decompose, get aluminium hydroxide; Get aluminum oxide behind the Aluminium hydroxide roasting.
Further, in step e, described raw material agglomerating prescription is: concentrate, yellow soda ash, also comprise in these the two kinds of materials of causticization slag after lime or the pre-desiliconization mother liquor causticization one or both, according to mol ratio Ca: Si=1.9～2.5, mol ratio Na: (Al+Fe)=0.95～1.05 carry out proportioning.
Further, in step e, described raw material agglomerating processing condition are: raw material are carried out sintering under 1100～1250 ℃, and constant temperature 15～120 minutes, it is grog for the 60-100 order that the cooling back is crushed to granularity with ball mill.
Further, in step D, described pre-desiliconization mother liquor goes the step of causticization to be: according to the mol ratio calcium oxide: sodium oxide is to carry out proportioning in 1: 1.1～1: 1.3, and lime is directly added in the pre-desiliconization mother liquor, after 1～2 hour, carry out solid-liquid separation at 95 ℃ of stirring reactions.
Further, in step B, the processing condition of described pre-desiliconization are, extraction is floated slurries behind the pearl 70～100 ℃ of pre-desiliconizations of following constant temperature 1.0～4.0 hours.
Further, in step F, the processing condition of described crude liquor of sodium aluminate deep desilication are: crude liquor of sodium aluminate adds calcium oxide according to the amount of 6～9 grams per liters, crude liquor of sodium aluminate is placed in the autoclave of sealing, keep mixing speed at 100～200 rev/mins, keep 140～160 ℃ of homo(io)thermism, react after 2 hours, the sodium aluminate filtrate that obtains is seminal fluid, and the siliceous modulus of this seminal fluid is greater than 400.
Further, in step C, described processing condition with hot water drip washing filter cake are: the temperature of hot water is 50～85 ℃, and the volume of every kilogram of dried used hot water of filter cake is 0.5 liter.
Further, in step C, described continuation circulation with the processing condition of hot sodium hydroxide solution or hot water drip washing filter cake is: the temperature of hot water or hot sodium hydroxide solution is 50～85 ℃, the mass percent concentration of sodium hydroxide solution is lower than 20%, the volume ratio of the quality of filter cake and hot sodium hydroxide solution or hot water is 1: 0.5, since drip washing second time filter cake, the filtrate behind the once washing filter cake of back is gone as the previous washing diluted sodium hydroxide solution of next round, by that analogy at every turn.
Further, in steps A, the concentration and the amount that add sodium hydroxide solution be, mass percent is to carry out proportioning in 1: 1.6～1: 8 according to the quality (kilogram) of flyash or slag and desiliconization in advance with the volume ratio (liter) of the broad liquid of annealing in hydrogen atmosphere sodium oxide between 10%～40%.
Further, in steps A, the processing condition of described stirring are: normal temperature starts whipping device down, and rotating speed keeps rotating 2～10 minutes at 20～50 rev/mins.
Further, in steps A, slag is ground to 200～250 orders.
Further, in step F, the temperature of described roasting is at 1050～1100 ℃.
Further, in step e, the processing condition that described grog and sodium carbonate solution carry out stripping are: with the grog that sinters, be 3～15 liters according to the volume of the every kilogram of used sodium carbonate solution of grog that sinters, the interpolation mass percent concentration is 4%～8%Na
2CO
3Solution, stripping is 15～60 minutes in 75 ℃～95 ℃ constant temperature.
Further, the method that pearl is floated in coproduction is, in steps A, after treating to float floating matter on the liquid level, opens floatation equipment and will float and collect in the dashpot after pearl is chosen, and just can obtain the white pearl product that floats through sorting once more, washing after the de-carbon operation.
Further, the method for co-producing white carbon black is:
In step D, with pre-desiliconization dope and with pre-desiliconization dope in the roughly suitable filter cake washing liquid of the content of sodium oxide and silicon-dioxide carry out the carbon branch after merging, carbon divided 2～3 hours in 60～95 ℃ of constant temperature, the control carbon dioxide flow, used carbonic acid gas body is 30～99% by long-pending fractional concentration, is carbon minute terminal point in the pH of aforesaid liquid value at 7.5～10.5 o'clock;
50～75 ℃ of following ageings is the white carbon black slurries after 15～60 minutes;
With the white carbon black slurries solid-liquid separation after the ageing; Collecting filtrate is pre-desiliconization mother liquor; Solid is a filter cake;
Pre-desiliconization mother liquor goes causticization: promptly according to the mol ratio calcium oxide: sodium oxide is to carry out proportioning in 1: 1.1～1: 1.3, lime is directly added in the pre-desiliconization mother liquor, at 95 ℃ of stirring reactions after 1～2 hour, carry out solid-liquid separation, solid filter cake is the causticization slag, main component is a lime carbonate, and filtrate is pre-desiliconization circulating mother liquor, directly as pre-desiliconization sodium hydroxide solution;
With 50～85 ℃ water wash filter cake, every kilogram of moisture filter cake need be used the 3-5 premium on currency, and filtrate collection is white carbon black one wash water, white carbon black one wash water, and usefulness in concentrate washing or white clay washing, filter cake is the white carbon black work in-process;
White carbon black work in-process process adds the hydrochloric acid of 2 mol or the sulfuric acid agitator treating of 2 mol purifies, washes the pH value with water between 5～8 then, filtrate collection after the washing is white carbon black two wash waters, in the white clay washing, use, the washing baking oven inner drying of white carbon black under 105～150 ℃ later, being controlled at time of drying after 1～3 hour is the white carbon black finished product.
Further, the method that magneticly elects smart iron sand from dry powder coal ash or slag is in steps A, directly to carry out magnetic separation with dry-type magnetic extractor after the grinding, magneticstrength is 1000～1300 oersteds, and the mass percent of ferric oxide is about 45% in the iron washed ore of acquisition; Through after taking off the magnetic machine demagnetization, carry out magnetic separation through the one-level magnetic plant again behind 45% the iron washed ore, magneticstrength is 900～1050 oersteds, and the mass percent of ferric oxide is about 65% in the final iron washed ore that obtains.
Further, the method for jointly producing cement is:
In step e, earlier with 50～85 ℃ pure water drip washing filter cake, every kilogram of used pure water of dried filter cake is 0.5 liter, and with the filtrate collection behind the drip washing first time filter cake, merging together with filtrate after grog stripping slurries separate afterwards is crude liquor of sodium aluminate;
Continue to repeat water or white carbon black one wash water or white carbon black two wash water drip washing filter cakes with 50～85 ℃, the volume of every kilogram of dried used liquid of filter cake is with for the first time identical, filtrate behind the once washing filter cake of back is gone as the previous pouring scouring water of next round at every turn, to the last in filtrate behind the once washing and the crude liquor of sodium aluminate sodium oxide and alumina content roughly quite after, with the filtrate collection after this washing, and with the crude liquor of sodium aluminate deep desilication; Change other white carbon black one wash water and white carbon black two wash waters or hot water again and continue filter cake is washed, sodium oxide mass percentage content＜7% in white clay stops washing; Through the oven dry of the filter cake after the washing, be white clay;
Then according to quality than white clay: lime is 5: 1～1: 1 ratio batching, enters the manufacture of cement operation and produces cement.
The present invention improves in the following areas:
1, organically continuously, the smart iron sand in stage-by-stage extraction flyash or the slag, float pearl, metallurgical-grade aluminum oxide, white carbon black, and the whole system technical process of jointly producing cement;
2, the processing condition of flyash or the pre-desiliconization of slag, alumina silica ratio in the concentrate after raising flyash or the pre-desiliconization of slag;
3, after the pre-desiliconization carbon mother liquid causticization in its solution the NaOH mass percent concentration 10～16%, can directly be used to pre-desiliconization, need not concentrate fully, greatly cut down the consumption of energy, compare the pre-desiliconization technology of other flyash, from white carbon black, extract one ton of white carbon black, approximately can reduce by 3 tons of standard coals/ton white carbon black energy consumption;
4, the optimization of concentrate raw material sintering prescription and sintering process condition not only makes energy consumption reduce, and (solubility rate is meant useful component Na in the concentrate also to have improved solubility rate
2O and AL
2O
3The amount that stripping comes in process in leaching is a call general in the alumina industry);
5, sintered clinker dissolving-out process condition has improved solubility rate;
6, the separation of concentrate, circulation cleaning technology;
7, crude sodium aluminate liquid deep desilication technology, energy consumption has been saved in repeatedly desiliconization;
8, cement is produced in the white clay coproduction.
Beneficial effect of the present invention is:
1, by flyash or the pre-desilication process of slag, improved the alumina silica ratio in the concentrate, promoted the taste of flyash or slag as bauxite resource, extract aluminum oxide for flyash or slag utilization and opened up new road, and greatly reduced flyash or slag and extracted the waste residue amount that produces behind the aluminum oxide, compare directly and extract the output that aluminum and coproducing cement has significantly reduced cement, reduced the waste residue intractability with flyash or slag;
2, from flyash or slag, extract aluminum oxide with reasonable method, both widened the source channel of aluminum oxide, alleviate the disparities between supply and demand of China's aluminum oxide to a certain extent, can save bauxite resource again, containment China bauxite resource quickens exhausted trend, and can remedy the deficiency of western China bauxite resource, and change the unbalanced Distribution Pattern of China's bauxite resource, greatly alleviated the shortage of China's bauxite resource.
[description of drawings]
Fig. 1 is a general flow chart of the present invention.
[embodiment]
In order to make those skilled in the art can further understand feature of the present invention and technology contents, see also following about detailed description of the present invention and accompanying drawing, accompanying drawing only provide with reference to and explanation, be not to be used for limiting the present invention.
Below in conjunction with accompanying drawing, embodiments of the present invention are described.
As shown in Figure 1, when from flyash or slag, extracting metallurgical-grade aluminum oxide, can realize by following steps:
101: slag is ground to 200～250 orders, dry powder coal ash or slag are carried out magnetic separation with dry-type magnetic extractor, magneticstrength is 1000～1300 oersteds, and the mass percent of ferric oxide is about 45% in the iron washed ore of acquisition; Through taking off the magnetic machine demagnetization, carry out magnetic separation through the one-level magnetic plant more again, magneticstrength is 900～1050 oersteds, and the mass percent of ferric oxide is about 65% in the final iron washed ore that obtains.
102: with flyash after the magnetic separation or slag, with mass percent 10%～40% NaOH solution, according to solid-to-liquid ratio: i.e. flyash quality (kilogram) and pre-desiliconization is to carry out proportioning in 1: 1.6～1: 8 with the volume ratio (liter) of the broad liquid of sodium hydroxide, normal temperature starts whipping device down, rotating speed is at 20～50 rev/mins, keep rotating 2～10 minutes, after treating to float floating matter on the liquid level, open floatation equipment and will float and collect in the dashpot after pearl is chosen, just can obtain the white pearl product that floats through sorting once more, washing after the de-carbon operation;
103: extraction is floated the molten slurries of flyash behind the pearl or slag and sodium hydroxide 70～100 ℃ of pre-desiliconizations of following constant temperature after 1.0～4.0 hours, pre-desiliconization slurries;
104: pre-desiliconization slurries solid-liquid separation, liquid portion is pre-desiliconization filtrate, and solid part is a filter cake, with 50～85 ℃ water wash filter cake; Solid-to-liquid ratio (down with), promptly the volume (every liter) of filter cake quality (every kilogram of dry product) and institute's water is than being 1: 0.5; With the filtrate collection behind the drip washing first time filter cake, merge afterwards standby together with the filtrate after pre-desiliconization slurries separate for pre-desiliconization dope, 50～85 ℃ the mass percent concentration that continues usefulness is lower than 20% diluted sodium hydroxide solution or hot water drip washing filter cake, solid-to-liquid ratio still is 1: 0.5, filtrate behind the once washing filter cake of back is gone as the previous washing diluted sodium hydroxide solution of next round at every turn, such as the diluted sodium hydroxide solution that will use as next round drip washing for the first time filter cake behind the filtrate collection after the secondary washing, wash the diluted sodium hydroxide solution of usefulness for the second time as next round behind the filtrate collection after the washing for the third time, and the like, to the last in the filtrate behind the once washing and the pre-desiliconization dope sodium oxide and silica content roughly quite after, with the filtrate collection behind the last washing leaching cake, and merge with pre-desiliconization dope, carbon elimination divides the preparation white carbon black to go together; Changing other hot sodium hydroxide solution or hot water again continues filter cake is washed, quality percentage composition＜8.8% of sodium oxide in filter cake, stop filter cake washing, through the oven dry of the filter cake after the washing, be concentrate, the alumina silica ratio of concentrate (mass ratio of aluminum oxide and silicon oxide) is 1.4: 1～1.6: 1, is used as the bauxite resource of soda-lime (stone) sintering process.
105: with pre-desiliconization dope and with pre-desiliconization dope in the roughly suitable filter cake washing liquid of the content of sodium oxide and silicon-dioxide merge, carbon divided 2～3 hours in 60～95 ℃ of constant temperature, the control carbon dioxide flow, used gas concentration lwevel 30～99% (volume fraction) was carbon minute terminal point in the pH of aforesaid liquid value at 7.5～10.5 o'clock;
Aforesaid liquid 50～75 ℃ of following ageings (ageing be meant reaction finish after with the material precipitation fully after, allow the precipitation that just generates place for some time with mother liquor, this process is called " ageing ") be the white carbon black slurries after 15～60 minutes;
106: with the white carbon black slurries solid-liquid separation after the ageing, collecting filtrate is pre-desiliconization mother liquor, and solid is a filter cake;
Pre-desiliconization mother liquor goes causticization, and promptly according to the mol ratio calcium oxide: sodium oxide is to carry out proportioning in 1: 1.1～1: 1.3, and lime is directly added in the pre-desiliconization mother liquor, at 95 ℃ of stirring reactions after 1～2 hour, carry out solid-liquid separation, solid filter cake is the causticization slag, and main component is a lime carbonate; Filtrate is pre-desiliconization circulating mother liquor, and directly (ultimate principle of causticizing reaction is shown in the following reaction equation: CaO+H with sodium hydroxide solution as pre-desiliconization
2O=Ca (OH)
2, Na
2CO
3+ Ca (OH)
2=2NaOH+CaCO
3↓, NaHCO
3+ Ca (OH)
2=NaOH+CaCO
3↓+H
2O);
With 50～85 ℃ water wash filter cake of solid-to-liquid ratio 1: 3～1: 5 (quality of moisture filter cake and the volume ratio of bath water), promptly the moisture filter cake of per kilogram need be used the 3-5 premium on currency; Filtrate collection be white carbon black one wash water standby (this filtrate can be used for washing filter cakes behind the pre-desilication reaction, also can be used for subsequent oxidation aluminium produce in the washing of white clay), filter cake is the white carbon black work in-process;
White carbon black work in-process (filter cake) process adds the hydrochloric acid of 2 mol or the sulfuric acid agitator treating of 2 mol purifies, washes the pH value with water 5～8 then, filtrate collection after the washing is white carbon black two wash waters, be used for the washing of alumina producing white clay, the washing baking oven inner drying of white carbon black under 105～150 ℃ later, being controlled at time of drying after 1～3 hour is the white carbon black finished product, and its physico-chemical property is: the DBP absorption value is greater than 2.32cm
3/ g, nitrogen adsorption specific surface area are greater than 190m
2/ g, pH value are 5.3～7.9, weight loss on heating is 4.1%～7.4%;
107: with concentrate, yellow soda ash, and in these the two kinds of materials of causticization slag after lime or the pre-desiliconization mother liquor causticization one or both, according to Ca: Si (being called for short the calcium ratio) is 1.9～2.5 (mol ratios), Na: (Al+Fe) (being called for short the alkali ratio) is that 0.95～1.05 (mol ratio) proportioning is dry grinded, mixing is raw material; Raw material are carried out sintering at 1100～1250 ℃, and constant temperature 15～120 minutes, it is that 60～100 orders are standby sintered clinker that the cooling back is crushed to granularity with ball mill;
108: with the grog that sinters, the volume ratio of the sodium carbonate solution of using according to clinker quality that sinters and stripping (quality is by every kilogram, and volume is by every liter) is 1: 3～1: 15, interpolation 4%～8% (mass percent concentration) Na
2CO
3Solution, stripping is 15～60 minutes in 75 ℃～95 ℃ constant temperature;
109: with the solid-liquid separation after the stripping, filtrate collection, solid filter cake be with 50～85 ℃ water wash, and the volume (liter) of filter cake quality (per kilogram dry product) and institute's water is than being 1: 0.5;
With the filtrate collection behind the drip washing first time filter cake, merge the back together with filtrate after grog stripping slurries separate and be crude liquor of sodium aluminate;
Continue circulation with 1: 0.5 white carbon black one wash water of solid-to-liquid ratio or white carbon black two wash waters (or water, promptly water replenishes when the white carbon black wash water is not enough) 50～85 ℃ of water wash filter cakes, filtrate behind the once washing filter cake of back is gone as the previous washing liquid of next round at every turn, such as the washing lotion that will use as next round drip washing for the first time filter cake behind the filtrate collection after the secondary washing, wash the washing lotion of usefulness for the third time behind the filtrate collection after the washing for the second time as next round, and the like, to the last in filtrate behind the once washing and the crude liquor of sodium aluminate sodium oxide and alumina content roughly quite after, with the filtrate collection behind the last washing leaching cake, and merge with crude liquor of sodium aluminate, come along deep desilication; Change other white carbon black one wash water and white carbon black two wash waters or hot water again and continue filter cake is washed, sodium oxide mass percentage content＜7% in white clay stops washing; Through the oven dry of the filter cake after the washing, be white clay;
110: the filtrate behind crude liquor of sodium aluminate and the last washing leaching cake together, amount according to 6～9 grams per liters adds calcium oxide, be placed in the autoclave of sealing, keep mixing speed at 100～200 rev/mins, keep 140～160 ℃ of homo(io)thermism, react after 2 hours, the liquid that obtains is seminal fluid, and the siliceous modulus of this seminal fluid is greater than 400 (siliceous modulus is meant the ratio of mass concentration with the mass concentration of silicon of aluminum oxide);
111: (flue gas cleaning is that sintering process is produced method in common in the aluminum oxide, generally makes its dustiness reduce to 0.03g/m by modes such as electrostatic precipitations after purifying with Wingdale kiln gas
3) import sodium aluminate concentrate solution is carried out the carbonating decomposition, get aluminium hydroxide;
112: aluminium hydroxide 1050～1100 ℃ of following roastings, is got aluminum oxide, its impurity component (mass percent): silicon oxide＜0.04%, sodium oxide＜0.65%;
113: according to white clay: the mass ratio of lime is 5: 1～1: 1 a ratio batching, enters the manufacture of cement operation and produces cement.
Below tabulation is 11 embodiment according to above flow process, and each embodiment has listed the data of the processing condition in above-mentioned flow process, and the quantum of output of aluminum oxide and other coproduction products.
Illustrate: 1, latter two embodiment is a feather weight;
2, selected smart iron sand ferric oxide quality percentage composition is 65%.
Present method has realized flyash or slag resource utilization, minimizing, substep has been chosen smart iron sand in flyash or the slag, has been floated pearl, white carbon black and aluminum oxide have been extracted, and with residue white clay utilization production cement, greatly improve the added value of flyash or slag deep processing, one ton of selectable smart iron sand 15～18kg of flyash, float pearl 2.0～2.5kg, white carbon black 130～150kg, aluminum oxide 280～350kg;
Present method has also adapted to national Economic development new strategy, from flyash or slag, extract continuously smart iron sand, float that materials such as water, carbonic acid gas, caustic soda, soda ash all can be recycled in the whole technological process of pearl, silicon oxide and metallurgical-grade aluminum oxide, energy consumption and material consumption are significantly reduced.For the west area that water resources lacks relatively, the saving of water resources has more importantly meaning undoubtedly.In addition, the discharging of no poisonous, harmful waste does not produce new pollution in the whole technological process, meets the requirement that recycling economy is set up in national Eleventh-Five Year Plan fully, realize the cleaner production that flyash or slag utilize, embodied the perfect unity of environmental benefit, ecological benefits and social benefit.
The above only is embodiments of the present invention, be not so promptly limit claim of the present invention, the equivalent transformation that every utilization specification sheets of the present invention and accompanying drawing content are done directly or indirectly is used in other relevant technical field, all in like manner is included in the claim of the present invention.
Claims (17)
1. method of extracting metallurgical-grade aluminum oxide from flyash or slag may further comprise the steps:
Steps A:, stir behind the adding sodium hydroxide solution with the slag after dry powder coal ash or the grinding;
Step B:, get pre-desiliconization slurries with the pre-desiliconization of slurries;
Step C: solid-liquid separation and concentrate washing: pre-desiliconization slurries solid-liquid separation, liquid portion is pre-desiliconization filtrate, solid part is a filter cake, with hot water drip washing filter cake, with the filtrate collection behind the drip washing filter cake, merge the back pre-desiliconization dope that is together with the filtrate after pre-desiliconization slurries separate, continue to circulate with hot sodium hydroxide solution or hot water drip washing filter cake, filtrate after to the last the content of sodium oxide and silicon-dioxide roughly will wash after quite for the last time in the filtrate behind the once washing and the pre-desiliconization dope merges with pre-desiliconization dope, changing other hot sodium hydroxide solution or hot water again continues filter cake is washed, quality percentage composition＜8.8% of sodium oxide in filter cake, stop filter cake washing, through the oven dry of the filter cake after the washing, be concentrate, the aluminum oxide of concentrate and the mass ratio of silicon oxide are 1.4:1～1.6:1;
Step D: with pre-desiliconization dope and with pre-desiliconization dope in filtrate after the roughly suitable filter cake washing of the content of sodium oxide and silicon-dioxide carry out obtaining being the white carbon black slurries after carbon branch, the ageing that collecting filtrate after the white carbon black slurries solid-liquid separation is pre-desiliconization mother liquor after merging; After pre-desiliconization mother liquor went causticization, solid filter cake was the causticization slag, and filtrate is pre-desiliconization circulating mother liquor, directly as pre-desiliconization sodium hydroxide solution;
Step e: with causticization slag and the yellow soda ash after concentrate, lime or the pre-desiliconization mother liquor causticization, dry grind, mixing is raw material, is grog behind the raw material sintering, grog and sodium carbonate solution carry out stripping; Carry out solid-liquid separation after the stripping, solid is a filter cake, and liquid is filtrate, and filtrate collection is a crude liquor of sodium aluminate, is that white clay is standby after the filter cake washing;
Step F: behind the deep desilication of crude liquor of sodium aluminate, carry out carbonating and decompose, get aluminium hydroxide; Get aluminum oxide behind the Aluminium hydroxide roasting.
2. a kind of method as claimed in claim 1, it is characterized in that, in step e, described raw material agglomerating prescription is: concentrate, yellow soda ash, also comprise a kind of in these the two kinds of materials of causticization slag after lime or the pre-desiliconization mother liquor causticization, according to mol ratio Ca:Si=1.9～2.5, mol ratio Na:(Al+Fe)=0.95～1.05 carry out proportioning.
3. a kind of method as claimed in claim 1, it is characterized in that in step e, described raw material agglomerating processing condition are: raw material are carried out sintering under 1100～1250 ℃, and constant temperature 15～120 minutes, it is that 60～100 orders are grog that the cooling back is crushed to granularity with ball mill.
4. a kind of method as claimed in claim 1, it is characterized in that, in step D, described pre-desiliconization mother liquor goes the step of causticization to be: according to the mol ratio calcium oxide: sodium oxide is that 1:1.1～1:1.3 carries out proportioning, lime is directly added in the pre-desiliconization mother liquor, after 1～2 hour, carry out solid-liquid separation at 95 ℃ of stirring reactions.
5. a kind of method as claimed in claim 1 is characterized in that, in step B, the processing condition of described pre-desiliconization are, extraction is floated slurries behind the pearl 70～100 ℃ of pre-desiliconizations of following constant temperature 1.0～4.0 hours.
6. a kind of method as claimed in claim 1, it is characterized in that, in step F, the processing condition of described crude liquor of sodium aluminate deep desilication are: crude liquor of sodium aluminate adds calcium oxide according to the amount of 6～9 grams per liters, crude liquor of sodium aluminate is placed in the autoclave of sealing, keeps mixing speed at 100～200 rev/mins, keep 140～160 ℃ of homo(io)thermism, react after 2 hours, the sodium aluminate filtrate that obtains is seminal fluid, and the siliceous modulus of this seminal fluid is greater than 400.
7. a kind of method as claimed in claim 1 is characterized in that, in step C, described processing condition with hot water drip washing filter cake are: the temperature of hot water is 50～85 ℃, and the volume of every kilogram of dried used hot water of filter cake is 0.5 liter.
8. a kind of method as claimed in claim 1, it is characterized in that, in step C, described continuation circulation with the processing condition of hot sodium hydroxide solution or hot water drip washing filter cake is: the temperature of hot water or hot sodium hydroxide solution is 50～85 ℃, the mass percent concentration of sodium hydroxide solution is lower than 20%, the volume ratio of the quality of filter cake and hot sodium hydroxide solution or hot water is 1:0.5, since drip washing second time filter cake, each with the filtrate behind the once washing filter cake of back as the previous washing diluted sodium hydroxide solution of next round, by that analogy.
9. a kind of method as claimed in claim 1, it is characterized in that, in steps A, the concentration and the amount that add sodium hydroxide solution are, mass percent is between 10%～40%, is that 1:1.6～1:8 carries out proportioning according to the quality of flyash or slag and pre-desiliconization with the volume ratio of sodium hydroxide solution, and described mass unit be a kilogram, and described volume unit is a liter.
10. a kind of method as claimed in claim 1 is characterized in that, in steps A, the processing condition of described stirring are: normal temperature starts whipping device down, and rotating speed keeps rotating 2～10 minutes at 20～50 rev/mins.
11. a kind of method as claimed in claim 1 is characterized in that, in steps A, slag is ground to 200～250 orders.
12. a kind of method as claimed in claim 1 is characterized in that, in step F, the temperature of described roasting is at 1050～1100 ℃.
13. a kind of method as claimed in claim 1, it is characterized in that, in step e, the processing condition that described grog and sodium carbonate solution carry out stripping are: with the grog that sinters, volume according to the every kilogram of used sodium carbonate solution of grog that sinters is 3～15 liters, and the interpolation mass percent concentration is 4%～8%Na
2CO
3Solution, stripping is 15～60 minutes in 75 ℃～95 ℃ constant temperature.
14. a kind of method as claimed in claim 1, it is characterized in that, the method that pearl is floated in coproduction is, in steps A, after the stirring, after treating to float floating matter on the liquid level, open floatation equipment and will float and collect in the dashpot after pearl is chosen, just can obtain the white pearl product that floats through sorting once more, washing after the de-carbon operation.
15. a kind of method as claimed in claim 1 is characterized in that, the method for co-producing white carbon black is:
In step D, with pre-desiliconization dope and with pre-desiliconization dope in the roughly suitable filter cake washing liquid of the content of sodium oxide and silicon-dioxide carry out the carbon branch after merging, carbon divided 2～3 hours in 60～95 ℃ of constant temperature, the control carbon dioxide flow, used carbonic acid gas by volume fractional concentration is 30～99%, is carbon minute terminal point in the pH of aforesaid liquid value at 7.5～10.5 o'clock;
50～75 ℃ of following ageings is the white carbon black slurries after 15～60 minutes;
With the white carbon black slurries solid-liquid separation after the ageing; Collecting filtrate is pre-desiliconization mother liquor; Solid is a filter cake;
Pre-desiliconization mother liquor goes causticization: promptly according to the mol ratio calcium oxide: sodium oxide is that 1:1.1～1:1.3 carries out proportioning, lime is directly added in the pre-desiliconization mother liquor, at 95 ℃ of stirring reactions after 1～2 hour, carry out solid-liquid separation, solid filter cake is the causticization slag, main component is a lime carbonate, and filtrate is pre-desiliconization circulating mother liquor, directly as pre-desiliconization sodium hydroxide solution;
With 50～85 ℃ water wash filter cake, every kilogram of moisture filter cake need be used the 3-5 premium on currency, and filtrate collection is white carbon black one wash water, white carbon black one wash water, and usefulness in concentrate washing or white clay washing, filter cake is the white carbon black work in-process;
White carbon black work in-process process adds the hydrochloric acid of 2 mol or the sulfuric acid agitator treating of 2 mol purifies, washes the pH value with water between 5～8 then, filtrate collection after the washing is that white carbon black two wash waters are used in the white clay washing, the washing baking oven inner drying of white carbon black under 105～150 ℃ later, being controlled at time of drying after 1～3 hour is the white carbon black finished product.
16. a kind of method as claimed in claim 1, it is characterized in that, the method that magneticly elects smart iron sand from dry powder coal ash or slag is, in steps A, slag after dry powder coal ash or the grinding directly carries out magnetic separation with dry-type magnetic extractor, magneticstrength is 1000～1300 oersteds, and the mass percent of ferric oxide is 45% in the iron washed ore of acquisition; Through after taking off the magnetic machine demagnetization, carry out magnetic separation through the one-level magnetic plant again behind 45% the iron washed ore, magneticstrength is 900～1050 oersteds, and the mass percent of ferric oxide is 65% in the final iron washed ore that obtains.
17. a kind of method as claimed in claim 15 is characterized in that, the method for jointly producing cement is:
In step e, earlier with 50～85 ℃ pure water drip washing filter cake, every kilogram of used pure water of dried filter cake is 0.5 liter, and with the filtrate collection behind the drip washing first time filter cake, merging together with filtrate after grog stripping slurries separate afterwards is crude liquor of sodium aluminate;
Continue to repeat water or white carbon black one wash water or white carbon black two wash water drip washing filter cakes with 50～85 ℃, the volume of every kilogram of dried used liquid of filter cake is with for the first time identical, filtrate behind the once washing filter cake of back is gone as the previous pouring scouring water of next round at every turn, to the last in filtrate behind the once washing and the crude liquor of sodium aluminate sodium oxide and alumina content roughly quite after, with the filtrate collection after this washing, and with the crude liquor of sodium aluminate deep desilication; Change other white carbon black one wash water and white carbon black two wash waters or hot water again and continue filter cake is washed, the mass percentage content of sodium oxide＜7% in white clay stops washing; Through the oven dry of the filter cake after the washing, be white clay;
Then according to quality than white clay: lime is the ratio batching of 5:1～1:1, enters the manufacture of cement operation and produces cement.
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| CN101811712A (en) | 2010-04-27 | 2010-08-25 | 中国神华能源股份有限公司 | Method for preparing metallurgical-grade aluminum oxide by using fluid-bed fly ash |
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| CN106986369B (en) * | 2017-04-08 | 2018-07-06 | 广西凤山县五福矿业发展有限公司 | The method that gypsum is prepared during low iron aluminium concentrate synthetical recovery |
| CN107177740B (en) * | 2017-05-16 | 2020-01-24 | 河钢股份有限公司承德分公司 | Method for recovering aluminum from refining slag |
| CN109231245A (en) * | 2018-09-26 | 2019-01-18 | 中南大学 | A kind of desilication method of silicon-aluminum containing material |
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