CN101306426A - Method for extracting iron washed ore from fly ash or slag - Google Patents
Method for extracting iron washed ore from fly ash or slag Download PDFInfo
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- CN101306426A CN101306426A CNA2008101153583A CN200810115358A CN101306426A CN 101306426 A CN101306426 A CN 101306426A CN A2008101153583 A CNA2008101153583 A CN A2008101153583A CN 200810115358 A CN200810115358 A CN 200810115358A CN 101306426 A CN101306426 A CN 101306426A
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Abstract
The invention relates to a method for the comprehensive utilization of fly ash and slag, in particular to a method for extracting the iron concentrate ore from the fly ash or the slag. The method comprises the technological processes as follows: a screening process of the iron concentrate ore in the fly ash or the slag, a flotation process of floating beads, a pre-desiliconization process, a technological process of white carbon black production, a technological process of alumina production and a technological process of cement production by adopting the slag. Since the element Fe in the fly ash or the slag is not uniformly distributed, the fly ash or the slag is ground by a ball mill so as to allow the extracted iron ore to meet certain requirements for the quality and the purity; and the purity of the iron ore can be further improved after dry magnetic separation of two levels. Moreover, after the iron concentrate ore is extracted, the floating beads, the white carbon black, alumina and joint cement can also be extracted from the fly ash or the slag organically and continuously step by step.
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 iron washed ore.
[background technology]
Flyash is a kind of solid particle aggregate of high degree of dispersion, and the chemical analysis of flyash or slag is relevant with the mineral composition of coal. physical property changes with differences such as coal and boiler shape, combustion systems.This method adopts the aluminous fly-ash of China and west Mongolia or slag to extract iron ore.
Iron in flyash or the slag mainly is the tiny spherolite that is made of the solid solution structure pyrite, bloodstone, siderite, limonite etc.Generally all contain iron-bearing minerals such as pyrite, marcasite, lazulite in the coal, so contain a certain amount of iron in its burning products therefrom.Be subjected to source, the kind of coal, the influence of coal combustion situation, the amount of different fly ash in electric power plant or slag institute iron content is different.In the various compositions in flyash or slag, its proportion maximum has magnetic. and be pitchy, be different from other fly ash grain.A part has magnetic though the iron ore material that contains in the coal a lot, has only seldom, and major part is non magnetic, can not directly carry out magnetic separation with magnetic separator.Coal is through boiler combustion, under the reduction of carbon and carbon monoxide, some can form granulated iron, and another part non magnetic ore is reduced into and is Armco magnetic iron, thereby the iron that can separate in flyash or the slag with the method for magnetic separation mainly is with titanomagnetite [(TiO
2) FeOFe
2O
3], Fe
3O
4And bloodstone (Fe
2O
3) the form existence.
In recent years, most of achievement in research of extracting useful resources both at home and abroad from flyash or slag only has theory significance, the main cause that limits these achievement in research industrialization is that not system is studied in the extraction of flyash or slag useful resources, for example, some is research extraction aluminium oxide separately, some specialize in the extraction silica, some special iron washed ore 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, do not carry out the extraction of resource interrelated, integrate, and make it to become a feasible overall plan, and make extraction cost high, be difficult to carry out Industry Promotion.
[summary of the invention]
Given this, this patent proposes a kind of method that flyash behind the fired coal combustion of thermal power plant or slag is extracted the iron washed ore raw material.This method through behind the ball mill grinding, makes the quality and the purity of the iron ore that flyash or cinder extract reach certain requirement in slag, and through the two-stage dry type magnetic separation, can further improve the purity of iron ore.
For achieving the above object, the invention provides a kind of from from flyash or slag, extracting the method for iron washed ore, comprising following steps:
Step 1: slag at first grinds;
Step 2: the slag after flyash or the grinding is carried out magnetic separation with dry-type magnetic extractor, obtain the iron washed ore semi-finished product;
Step 3: the iron washed ore semi-finished product are through taking off the magnetic machine demagnetization;
Step 4: after carrying out magnetic separation through the one-level magnetic plant again, obtain iron washed ore.
Further, in step 1, the equipment of described grinding is agitating ball mill.
Further, in step 1, the fineness of described grinding is about 200～250 orders.
Further, in step 2, the magnetic field intensity of described magnetic separation is 1000～1300 oersteds.
Further, in step 2, the equipment of described demagnetization is portable demagnetizer.
Further, in step 3, the magnetic field intensity of described magnetic separation is 900～1050 oersteds.
Further, the method that pearl is floated in flyash or slag coproduction is, in step 2:
Flyash after the magnetic separation or slag are added sodium hydroxide solution, the concentration of sodium hydroxide solution be mass percent between 10%～40%, be to carry out proportioning in 1: 1.6～1: 8 according to the quality (kilogram) of flyash or slag and pre-desiliconization with the volume ratio (liter) of sodium hydroxide solution; Normal temperature starts mixing plant down then, and rotating speed keeps rotating 2～10 minutes at 20～50 rev/mins;
After treating to float floating thing on the liquid level, the unlatching floatation equipment will float to be collected in the dashpot after pearl is chosen;
Float that pearl is collected after the de-carbon operation, just can obtain the white pearl product that floats through sorting once more, washing again.
Further, flyash or slag coproduction method of alumina are that after pearl was floated in extraction, flyash or slag carried out following steps with the slurries of sodium hydroxide solution:
Steps A: pre-desiliconization: get pre-desiliconization slurries after 1.0～4.0 hours 70～100 ℃ of pre-desiliconizations of following constant temperature;
Step B: Separation of Solid and Liquid and filter cake washing: pre-desiliconization slurries Separation of Solid and Liquid, liquid partly is pre-desiliconization filtrate, and solid portion is a filter cake;
With 50～85 ℃ water wash filter cake, the volume of every kilogram of dried used hot water of filter cake is 0.5 liter, and the filtrate behind the drip washing first time filter cake is collected, and merging the back together with pre-desiliconization filtrate after pre-desiliconization slurries separate is pre-desiliconization dope;
Continue to circulate with hot sodium hydroxide solution or hot water drip washing filter cake: 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 (liter) of the quality of filter cake (kilogram) and hot sodium hydroxide solution or hot water is than being 1: 0.5, since drip washing second time filter cake, 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, by that analogy, to the last in the filtrate behind the once washing and the pre-desiliconization dope sodium oxide molybdena and dioxide-containing silica roughly quite after, itself and pre-desiliconization dope are merged, the raw material that divides the preparation white carbon as carbon, changing other hot sodium hydroxide solution or hot water again continues filter cake is washed, the mass percentage content of sodium oxide molybdena is lower than 8.8% in filter cake, stops filter cake being washed;
Through the oven dry of the filter cake after the washing, be concentrate, the aluminium oxide of concentrate and the mass ratio of silica are 1.4: 1～1.6: 1;
Step C: the preparation of causticization slag: with pre-desiliconization dope and with pre-desiliconization dope in the roughly suitable filter cake cleaning solution of the content of sodium oxide molybdena and silica carry out obtaining being the white carbon slurries after carbon branch, the ageing after merging; After the white carbon slurries Separation of Solid and Liquid after the ageing, collecting filtrate is pre-desiliconization mother liquor; Pre-desiliconization mother liquor goes causticization: promptly according to the mol ratio calcium oxide: sodium oxide molybdena 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, carries out Separation of Solid and Liquid at 95 ℃ of left and right sides stirring reactions, and solid filter cake is the causticization slag;
Step D: with described concentrate, sodium carbonate, 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, dry grind, be behind the mixing raw material;
Step e: described raw material are carried out sintering under 1100～1250 ℃, and constant temperature 15～120 minutes, it is to be grog about 60～100 orders that the cooling back is crushed to granularity with ball mill;
Step F: described grog and sodium carbonate liquor are carried out stripping, the volume of the sodium carbonate liquor that the required stripping of per kilogram grog that sinters is used is 3 liters～15 liters, the sodium carbonate liquor mass percent concentration is 4%～8%, and stripping is 15～60 minutes in 75 ℃～95 ℃ constant temperature;
Step G: with the Separation of Solid and Liquid after the stripping, filtrate is collected, and solid is a filter cake; With 50～85 ℃ pure water drip washing filter cake, every kilogram of used pure water of dried filter cake is 0.5 liter, the filtrate after collection of the filtrate behind the drip washing first time filter cake and the grog stripping slurries separated and collected is merged the back together be crude liquor of sodium aluminate;
Step H: continue to repeat with 50～85 ℃ white carbon one wash water or white carbon two wash waters or water (when above-mentioned wash water is not enough, use hot water) the drip washing filter cake, 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 molybdena and alumina content roughly quite after, filtrate after this washing is collected, and merge deep desilication with crude liquor of sodium aluminate; Change other white carbon one wash water and white carbon two wash waters or hot water at last again and continue filter cake is washed, the sodium oxide molybdena mass percentage content is lower than 7% in white clay, stops washing;
Step I: the process conditions 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 speed of agitator at 100～200 rev/mins, keep 140～160 ℃ of temperature constant, 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;
Step J: lime stone kiln gas is imported after purifying, sodium aluminate concentrate solution is carried out carbonating decompose, get aluminium hydroxide;
Step K:, get aluminium oxide with aluminium hydroxide roasting down about 1050～1100 ℃.
Further, the method for co-producing white carbon black is:
In step C, the filtrate of pre-desiliconization dope and last washing leaching cake is merged, and carbon divided 2～3 hours in 60～95 ℃ of constant temperature, the control carbon dioxide flow, used carbon dioxide body is 30～99% by the concentration of integration number, 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 slurries after 15～60 minutes;
With the white carbon slurries Separation of Solid and Liquid 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 molybdena 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 Separation of Solid and Liquid, solid filter cake is the causticization slag, main component is a calcium 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 is collected as white carbon one wash water, white carbon one wash water, and usefulness in concentrate washing or white clay washing, filter cake is the white carbon semi-finished product;
White carbon semi-finished product 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 after the washing is collected as white carbon two wash waters and uses in the white clay washing, the washing baking oven inner drying of white carbon under 105～150 ℃ later, being controlled at drying time after 1～3 hour is the white carbon finished product.
Further, the method for co-producing cement is:
In step H,, be white clay through the oven dry of the filter cake after the washing; According to quality than white clay: the ratio batching of lime=5: 1～1: 1 enters the manufacture of cement operation and produces cement.
The present invention improves in the following areas:
1, owing to the ferro element skewness in flyash or the cinder, can be behind the process ball mill grinding so that the quality and the purity of the iron ore that flyash or cinder extract reach certain requirement.
2,, can further improve the purity of iron ore through the two-stage dry type magnetic separation.
3, organically extract the iron washed ore in flyash or the slag, the whole system technological process of floating pearl, silica and aluminium oxide continuously, step by step;
4, the pre-desiliconization of flyash or slag, alumina silica ratio in the concentrate after the pre-desiliconization of raising flyash/slag;
5, 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 or slag, from white carbon, extract one ton of white carbon, approximately can reduce by 3 tons of standard coals/ton white carbon energy consumption;
6, the optimization of concentrate raw material sintering prescription and sintering process condition not only makes energy consumption reduce, and (dissolution rate is meant useful component Na in the concentrate also to have improved dissolution rate
2O and AL
2O
3The amount that stripping comes in process in leaching is a call general in the alumina industry);
7, sintered clinker dissolving-out process condition has improved dissolution rate;
8, the separation of concentrate, circulation cleaning technology;
9, crude sodium aluminate liquid deep desilication technology, energy consumption has been saved in repeatedly desiliconization;
10, cement is produced in the white clay coproduction.
Beneficial effect of the present invention is:
1, realizes the choosing of the iron oxide in flyash or the slag greatly improved the added value of flyash or slag deep processing;
2, by the iron selection technique in flyash or the slag, can obtain to smelt other iron ore of level, also can obtain the taste of flyash or slag as bauxite resource, extract aluminium oxide for flyash or slag utilization and opened up new road.Reduced flyash or slag and extracted the waste residue amount that produces behind the aluminium oxide, compared directly and extract the output that aluminum and coproducing cement has significantly reduced cement, reduced the waste residue intractability with flyash or slag.
[description of drawings]
Fig. 1 extracts the flow chart of iron washed ore for the present invention.
[specific 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 refined iron mine powder, can realize by following steps:
101: after at first using agitating ball mill JM-260 with slag fineness of grind to 200～250 orders, flyash need not grind;
102: flyash or grind after slag carry out magnetic separation with dry-type magnetic extractor XCGII120 * (30+30), magnetic field intensity is 1100～1300 oersteds, just can obtain to contain the crude iron washed ore of iron oxide (mass fraction) about 45%, output is about 3.5% of flyash or cinder quality.
103: the crude iron washed ore eliminates a part of namagnetic substance through taking off the portable demagnetizer demagnetization of magnetic machine DM160.
104: pass through again that one-level magnetic plant XCGII120 * (30+30), magnetic field intensity is 900～1050 oersteds, carry out to obtain to contain after the magnetic separation refined iron mine powder of iron oxide (mass fraction) about 65%.
Extract refined iron mine powder from flyash or slag after, this flow process is proceeded, and pearl, aluminium oxide, white carbon and cement raw material are floated in coproduction:
105: with flyash after the magnetic separation or slag, with mass percent 10%～40% NaOH solution, according to solid-to-liquid ratio: i.e. flyash or slag quality (kilogram) and pre-desiliconization is to carry out proportioning in 1: 1.6～1: 8 with the volume ratio (liter) of sodium hydroxide solution, normal temperature starts mixing plant down, rotating speed is at 20～50 rev/mins, keep rotating 2～10 minutes, treat to float on the liquid level to behind the floating thing, 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;
106: extraction is floated the molten slurries of flyash behind the pearl or slag and NaOH 70～100 ℃ of pre-desiliconizations of following constant temperature after 1.0～4.0 hours, pre-desiliconization slurries;
107: pre-desiliconization slurries Separation of Solid and Liquid, liquid partly is pre-desiliconization filtrate, and solid portion 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; Filtrate behind the drip washing first time filter cake is collected, to merge into pre-desiliconization dope together standby with the filtrate after pre-desiliconization slurries separate, 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 filtrate after the secondary washing being collected the diluted sodium hydroxide solution that the back is used as next round drip washing for the first time filter cake, filtrate after the washing is collected the diluted sodium hydroxide solution of back as next round second this washing usefulness for the third time, and the like, to the last the content of sodium oxide molybdena and silica roughly merges itself and pre-desiliconization dope after quite in the filtrate behind the once washing and the pre-desiliconization dope, and carbon elimination divides the preparation white carbon to go together; Changing other hot sodium hydroxide solution or hot water again continues filter cake to be washed Na in filter cake
2The quality percentage composition of O is lower than 8.8%, stops the filter cake washing, and through the oven dry of the filter cake after the washing, standby for concentrate, the alumina silica ratio of concentrate is 1.4: 1～1.6: 1, is used as the bauxite resource of soda lime (stone) sintering process.
108: with the filtrate after pre-desiliconization dope and the last washing, 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 a period of time with mother liquor, this process is called " ageing ") be the white carbon slurries after 15～60 minutes;
109: with the white carbon slurries Separation of Solid and Liquid after the ageing, collecting filtrate is pre-desiliconization mother liquor, and solid is a filter cake;
Pre-desiliconization mother liquor goes causticization, is to carry out proportioning in 1: 1.1～1: 1.3 according to mol ratio calcium oxide/sodium oxide molybdena promptly, and lime is directly added in the pre-desiliconization mother liquor, at 95 ℃ of stirring reactions after 1～2 hour, carry out Separation of Solid and Liquid, solid filter cake is the causticization slag, and main component is a calcium carbonate; Filtrate is pre-desiliconization circulating mother liquor, and (basic principle of causticizing reaction is shown in the following reaction equation to required sodium hydroxide solution: CaO+H during directly 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 slurry), promptly the moisture filter cake of per kilogram need be used the 3-5 premium on currency; Filtrate be collected as white carbon 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 semi-finished product;
White carbon semi-finished product (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 after the washing is collected as white carbon two wash waters, be used for the washing of alumina producing white clay, the washing baking oven inner drying of white carbon under 105～150 ℃ later, being controlled at drying time after 1～3 hour is the white carbon finished product, and its physicochemical 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, heating loss is 4.1%～7.4%;
110: with concentrate, sodium carbonate, 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), and 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;
111: with the grog that sinters, the volume ratio of the sodium carbonate liquor 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;
112: with the Separation of Solid and Liquid after the stripping, filtrate is collected, and solid filter cake is 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;
Filtrate behind the drip washing first time filter cake is collected, and merging the back together with filtrate after grog stripping slurries separate is crude liquor of sodium aluminate;
Continue circulation with 1: 0.5 white carbon one wash water of solid-to-liquid ratio or white carbon two wash waters (or water, promptly water replenishes when the white carbon 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 filtrate after the secondary washing being collected the washing lotion that the back is used as next round drip washing for the first time filter cake, filtrate after the washing is collected the back is washed usefulness for the second time as next round washing lotion for the third time, and the like, to the last in filtrate behind the once washing and the crude liquor of sodium aluminate sodium oxide molybdena and alumina content roughly quite after, filtrate behind the last washing leaching cake is collected, and merge with crude liquor of sodium aluminate, come along deep desilication; Change other white carbon one wash water and white carbon two wash waters or hot water at last again and continue filter cake is washed, sodium oxide content in white clay (mass percent) is lower than 7%, stops washing;
Through the filter cake oven dry after the washing, for white clay standby.
113: 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 speed of agitator at 100～200 rev/mins, keep 140～160 ℃ of temperature constant, 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 aluminium oxide);
114: (flue gas cleaning is that sintering process is produced method in common in the aluminium oxide, generally makes its dustiness reduce to 0.03g/m by modes such as electrostatic precipitations after purifying with lime stone kiln gas
3) import sodium aluminate concentrate solution is carried out the carbonating decomposition, get aluminium hydroxide;
115: aluminium hydroxide 1050～1100 ℃ of following roastings, is got aluminium oxide, its impurity component (mass percent) silica＜0.04%, sodium oxide molybdena＜0.65%;
116: 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 process conditions in above-mentioned flow process, and the quantum of output of aluminium oxide and other coproduction products.
Illustrate: latter two embodiment is a feather weight.
By above embodiment as can be seen, this method also realizes flyash or slag resource, minimizing, substep has been chosen iron oxide in flyash or the slag, has been floated pearl, white carbon and aluminium oxide have been extracted, and, greatly improve the added value of flyash or slag deep processing with residue white clay utilization production cement;
This method has also adapted to national economic development new strategy, from flyash or slag, extract continuously iron washed ore, float that materials such as water, carbon dioxide, NaOH, soda ash all can be recycled in the whole technical process of pearl, silica and metallurgical-grade aluminum oxide, energy consumption and material consumption are significantly reduced.For the west area that water resource lacks relatively, the saving of water resource has more importantly meaning undoubtedly.In addition, the discharging of no poisonous, harmful waste does not produce new pollution in the whole technical 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 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 (10)
1. method of extracting iron washed ore from flyash or slag may further comprise the steps:
Step 1: slag at first grinds;
Step 2: the slag after flyash or the grinding is carried out magnetic separation with dry-type magnetic extractor, obtain the crude iron ore in sand form;
Step 3: the iron washed ore semi-finished product are through taking off the magnetic machine demagnetization;
Step 4: after carrying out magnetic separation through the one-level magnetic plant again, obtain iron washed ore.
2. a kind of method as claimed in claim 1 is characterized in that, in step 1, the equipment of described grinding is agitating ball mill.
3. a kind of method as claimed in claim 1 is characterized in that, in step 1, the fineness of described grinding is 200～250 orders.
4. a kind of method as claimed in claim 1 is characterized in that, in step 2, the magnetic field intensity of described magnetic separation is 1100～1300 oersteds.
5. a kind of method as claimed in claim 1 is characterized in that, in step 2, the equipment of described demagnetization is portable demagnetizer.
6. a kind of method as claimed in claim 1 is characterized in that, in step 3, the magnetic field intensity of described magnetic separation is 900～1050 oersteds.
7. a kind of method as claimed in claim 1 is characterized in that, the method that pearl is floated in flyash or slag coproduction is, in step 2:
Flyash after the magnetic separation or slag are added sodium hydroxide solution, the concentration of sodium hydroxide solution be mass percent between 10%～40%, be to carry out proportioning in 1: 1.6～1: 8 according to the quality (kilogram) of flyash or slag and pre-desiliconization with the volume ratio (liter) of sodium hydroxide solution; Normal temperature starts mixing plant down then, and rotating speed keeps rotating 2～10 minutes at 20～50 rev/mins;
After treating to float floating thing on the liquid level, the unlatching floatation equipment will float to be collected in the dashpot after pearl is chosen;
Float that pearl is collected after the de-carbon operation, just can obtain the white pearl product that floats through sorting once more, washing again.
8. a kind of method as claimed in claim 7 is characterized in that, flyash or slag coproduction method of alumina are that after pearl was floated in extraction, flyash or slag carried out following steps with the slurries of sodium hydroxide solution:
Steps A: pre-desiliconization: get pre-desiliconization slurries after 1.0～4.0 hours 70～100 ℃ of pre-desiliconizations of following constant temperature;
Step B: Separation of Solid and Liquid and filter cake washing: pre-desiliconization slurries Separation of Solid and Liquid, liquid partly is pre-desiliconization filtrate, and solid portion is a filter cake;
With 50～85 ℃ water wash filter cake, the volume of every kilogram of dried used hot water of filter cake is 0.5 liter, and the filtrate behind the drip washing first time filter cake is collected, and merges back desiliconization dope in advance together with pre-desiliconization filtrate after pre-desiliconization slurries separate;
Continue to circulate with hot sodium hydroxide solution or hot water drip washing filter cake: 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 (liter) of the quality of filter cake (kilogram) and hot sodium hydroxide solution or hot water is than being 1: 0.5, since drip washing second time filter cake, 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, by that analogy, to the last in the filtrate behind the once washing and the pre-desiliconization dope sodium oxide molybdena and dioxide-containing silica roughly quite after, itself and pre-desiliconization dope are merged, the raw material that divides the preparation white carbon as carbon, changing other hot sodium hydroxide solution or hot water again continues filter cake to be washed Na in filter cake
2The mass percentage content of O＜8.8% stops filter cake being washed;
Through the oven dry of the filter cake after the washing, be concentrate, the aluminium oxide of concentrate and the mass ratio of silica are 1.4: 1-1.6: 1
Step C: the preparation of causticization slag: with pre-desiliconization dope and with pre-desiliconization dope in the roughly suitable filter cake cleaning solution of the content of sodium oxide molybdena and silica carry out obtaining being the white carbon slurries after carbon branch, the ageing after merging; After the white carbon slurries Separation of Solid and Liquid after the ageing, collecting filtrate is pre-desiliconization mother liquor; Pre-desiliconization mother liquor goes causticization: promptly according to the mol ratio calcium oxide: sodium oxide molybdena 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, carries out Separation of Solid and Liquid at 95 ℃ of left and right sides stirring reactions, and solid filter cake is the causticization slag;
Step D: with described concentrate, sodium carbonate, 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, dry grind, be behind the mixing raw material;
Step e: described raw material are carried out sintering under 1100～1250 ℃, and constant temperature 15～120 minutes, it is to be grog about 60～100 orders that the cooling back is crushed to granularity with ball mill;
Step F: described grog and sodium carbonate liquor are carried out stripping, the volume of the sodium carbonate liquor that the required stripping of per kilogram grog that sinters is used is 3 liters～15 liters, the sodium carbonate liquor mass percent concentration is 4%～8%, and stripping is 15～60 minutes in 75 ℃～95 ℃ constant temperature;
Step G: with the Separation of Solid and Liquid after the stripping, filtrate is collected, and solid is a filter cake; With 50～85 ℃ pure water drip washing filter cake, every kilogram of used pure water of dried filter cake is 0.5 liter, the filtrate after collection of the filtrate behind the drip washing first time filter cake and the grog stripping slurries separated and collected is merged the back together be crude liquor of sodium aluminate;
Step H: continue to repeat with 50～85 ℃ white carbon one wash water or white carbon two wash waters or water (when above-mentioned wash water is not enough, use hot water) the drip washing filter cake, 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 molybdena and alumina content roughly quite after, filtrate after this washing is collected, and with the crude liquor of sodium aluminate deep desilication; Change other white carbon one wash water and white carbon two wash waters or hot water at last again and continue filter cake is washed, the mass percent of sodium oxide molybdena is lower than 7% in white clay, stops washing;
Step I: the process conditions 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 speed of agitator at 100～200 rev/mins, keep 140～160 ℃ of temperature constant, 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;
Step J: lime stone kiln gas is imported after purifying, sodium aluminate concentrate solution is carried out carbonating decompose, get aluminium hydroxide;
Step K:, get aluminium oxide with aluminium hydroxide roasting down about 1050～1100 ℃.
9. a kind of method as claimed in claim 8 is characterized in that, the method for co-producing white carbon black is:
In step C, with pre-desiliconization dope and with pre-desiliconization dope in after the roughly suitable filter cake cleaning solution of the content of sodium oxide molybdena and silica merges, carbon divided 2～3 hours in 60～95 ℃ of constant temperature, the control carbon dioxide flow, used carbon dioxide body is 30～99% by the concentration of integration number, 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 slurries after 15～60 minutes;
With the white carbon slurries Separation of Solid and Liquid 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 molybdena 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 Separation of Solid and Liquid, solid filter cake is the causticization slag, main component is a calcium 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 is collected as white carbon one wash water, white carbon one wash water, and usefulness in concentrate washing or white clay washing, filter cake is the white carbon semi-finished product;
White carbon semi-finished product 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 after the washing is collected as white carbon two wash waters and uses in the white clay washing, the washing baking oven inner drying of white carbon under 105～150 ℃ later, being controlled at drying time after 1～3 hour is the white carbon finished product.
10. a kind of method as claimed in claim 8 is characterized in that, the method for co-producing cement is:
In step H,, be white clay through the oven dry of the filter cake after the washing; According to quality than white clay: the ratio batching of lime=5: 1～1: 1 enters the manufacture of cement operation and produces cement.
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