CN102311136A - Method for producing low iron aluminum sulfate by utilization of coal gangue - Google Patents

Method for producing low iron aluminum sulfate by utilization of coal gangue Download PDF

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CN102311136A
CN102311136A CN201110209467A CN201110209467A CN102311136A CN 102311136 A CN102311136 A CN 102311136A CN 201110209467 A CN201110209467 A CN 201110209467A CN 201110209467 A CN201110209467 A CN 201110209467A CN 102311136 A CN102311136 A CN 102311136A
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coal gangue
iron
acid
reaction
ace
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夏举佩
张召述
谷立轩
任雪娇
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/20Waste processing or separation

Abstract

The invention relates to a method for producing low iron aluminum sulfate by the utilization of coal gangue and belongs to the technical field of coal solid waste resource utilization. The method provided by the invention comprises the following steps of: carrying out calcination activation on coal gangue at the temperature of 785-850 DEG C, adjusting the pH of an aluminum sulfate solution by directly using the activated coal gangue, oxidizing divalent iron ions into trivalent ions, removing iron precipitate and a few gel in the aluminum sulfate solution by the utilization of the adsorption property of the coal gangue, producing low iron aluminum sulfate, recycling the removed iron slag, and terminating the recycling operation when the removed iron slag amount is greater than 120% of the acid-leach residue amount or the mass ratio of aluminium to iron in an iron-removing liquid is less than 160. The temperature of the calcinated coal gangue satisfies the operation condition for the boiling of a circulating fluidized bed. No addition of an auxiliary agent helps heat recovery. The activity of the coal gangue cinder is good, the grinding requirement is not high and the energy consumption is low. Hydrogen peroxide or ozone, air and variable valence element-containing hypervalent compounds KMnO4, MnO2 oxidizing agents are adopted to remove iron with less loss of aluminium. The ratio of Al2O3 to Fe in the product is greater than 160 and the quality of the product is high. The acid leaching reaction is carried out at normal pressure. And the production is easy to operate at low cost.

Description

A kind of method of utilizing the low iron Tai-Ace S 150 of coal gangue production
Technical field
The present invention relates to a kind of method of utilizing the low iron Tai-Ace S 150 of coal gangue production, belong to coal solid waste application technology as the second resource field.
Background technology
It is the developing country of main energy sources with coal that China is one; In primary energy consumption, coal accounts for more than 70%, and proportion exceeds more than a times of world average level; And in one quite long from now on period, it is main that the energy structure of China is still with coal.
Coal gangue is the solid waste that discharges in coal mining process and the coal washing process, be a kind of lower with a kind of carbon content of coal seam association in the coal-forming process, than the hard grey black look rock of coal.Comprise the spoil of choosing spoil and the coal washing process of extraction in top board, base plate and interlayer in digging gangue in the tunnelling process, the mining process of washing.Its staple is Al 2O 3, SiO 2, also contain the Fe that quantity does not wait in addition 2O 3, CaO, MgO, Na 2O, K 2O, P 2O 5, SO 3With micro-rare elements (gallium, vanadium, titanium, cobalt).Its quantity discharged is equivalent to about 10% of coal production then, totally stores up 4,500,000,000 tons at present, takes up an area of about 120,000 hectares, is one of maximum industry and mining solid waste of present China quantity discharged.A large amount of stackings of coal gangue; Not only cover the soil, influence ecological environment, spoil leaching water will pollute surrounding soil and underground water; And contain certain combustiblematerials in the coal gangue; Issue in suitable condition and to be conigenous combustion, obnoxious flavour pollutant atmospheres such as discharging sulfurous gas, oxynitride, oxycarbide and flue dust influence the healthy of mining area resident.
Along with continuing to increase of national environmental protection law enforcement dynamics; People are to the raising of environmental quality requirement; Solve the coal gangue environmental pollution problem and seem more and more outstanding, from the sixties, a lot of countries begin to pay attention to the processing and the utilization of coal gangue; It utilizes approach to summarize and mainly contains following several kinds: coal and pyrite are reclaimed in (1), and resistates is as material of construction; (2) be used for generating: main with washing coal and wash the cash multifuel combustion and generate electricity, about 2000 kilocalories of the every kg of mixture thermal value, slag can be produced cinder brick and slag cement; (3) make material of construction: substitute for clay utilizes the calorific value of coal gangue itself as brick-making raw material, practices thrift coal; (4) the substitute for clay component is produced Portland cement, sintering light skeletal; (5) coal gangue also can be used for producing low-heat value gas, makes pottery, makes soil improvement agent, or be used to pave the way, underground filling, ground filling make ground etc.Because the coal gangue place of production is all in remote mountain area; Make its utilization receive the restriction of transportation radius; The most effectively utilizing the way at present is to adopt suitable temperature of combustion to reclaim the heat generating, simultaneously the effective ingredient of burning in the slag is fully utilized, to realize coal gangue comprehensive utilization, minimizing discharging.
Tai-Ace S 150 is crucial basic industry raw material, is widely used as industries such as water purification agent, glue used in paper-making, foodstuff additive, petroleum cracking catalyzer, and the principal element that influences its quality is an iron level; The production of China's Tai-Ace S 150 is main with bauxite mainly at present; Technology commonly used is HTHP peracid amount, and the aluminium iron sulfate content that this method is produced is high, need carry out deferrization with methods such as chemical precipitation, extractions and handle; Production Flow Chart is long; Can produce secondary pollution simultaneously, high-quality Tai-Ace S 150 then need adopt the preparation of aluminium powder, white lake or aluminum oxide and acid-respons, and cost is higher.
Provide a kind of like patent CN1412115 and generated Tai-Ace S 150 with bauxitic clay and sulfuric acid pyroreaction in the compressive reaction still; This method bauxitic clay powder is-150 orders; Heat with chuck and to control reacting liquid temperature at 150 ℃~165 ℃, sulfuric acid concentration is 20%~25%; Patent CN1153141 reacts in reactor drum with aluminium-containing substances such as bauxite or aluminium ore powder or alum slag and sulfuric acid and produces liquid aluminium sulfate; Patent CN1153141 produces liquid aluminium sulfate with aluminium-containing substances such as bauxite or aluminium ore powder or alum slag and sulfuric acid at reactor reaction, and the aluminium-containing substance of weight percent 35%~55% aluminium sesquioxide and the weight percent of the vitriol oil are 98%~105%.Because domestic bauxite resource is abundant, and ore type is main with high silicon, high ferro, low alumina silica ratio and diaspore mainly, compares with countries such as Australia, Guinea, Jamaica easy molten gibbsitic bauxites, and tooling cost does not have advantage.Even like this, the bauxite resource of China with exploitation, utility value faced exhaustion in following 6~7 years.Therefore, seeking new aluminum oxide resource is the key of Chalco Sustainable development.
Containing higher aluminum oxide during coal measures is useless admittedly, is a kind of bauxite resource of tool potentiality.Alumina content and the forming process of coal in the coal gangue, peripheral geologic framework are relevant with mineral composition, general alumina content about 20%, China's southern area on the low side, the north like ground content such as Inner Mongol, Shanxi then up to about 40%.For this reason, many researchists have done number of research projects, have obtained to have the achievement of novelty.As: patent CN1048687 method of producing Tai-Ace S 150 with coal gangue; Coal gangue being carried out roasting, be ground into powdery, is 1 to 2.5 by dense stream acid than colliery powder; Diluting concentrated sulfuric acid becomes the diluted acid of 16~18Be to add in the colliery powder, at 120~140 ℃, 2~2.5kg/cm 2Reaction is 1.2-2 hour under the condition, removes slag through deposition, and quality product meets the rough secondary standard requirement of HG1-32-77; Patent CN1072657 method of producing Tai-Ace S 150 with coal gangue; Colliery powder is broken into powdery, without roasting, is that the sulfuric acid of 40~70% (weight) mixes in reactor drum with concentration directly; Stir, logical steam heats up and makes reactor pressure is 3.5~8kg/cm 2, reacted 4~6 hours, remove slag through sedimentation, condensing crystal gets white blocks of solid, and quality product meets the refining primary standard of HC1-32-77; Patent CN1174172 is a kind of method of producing Tai-Ace S 150 with coal gangue, through to coal gangue broken roasting, the cooling of coming out of the stove, leach, precipitate, filter, neutralize, refilter, concentrate, technological process such as crystallization gets product Tai-Ace S 150; Patent CN1915829 a kind ofly produces the method for Tai-Ace S 150, water glass and derived product thereof with coal gangue, and coal gangue is used the jaw crushing crusher machine, and organism is removed in roasting; Pulverize with ball mill; Make 80% through 200 mesh sieves, place the sulfuric acid of reaction kettle and concentration 40%~60% to react colliery powder, generate alum liquor; Again the alum liquor that generates is filtered, sends in the treatment tank, add barium sulphide BaS deironing; Patent CN1392109 is comprehensive utilization coal gangue coproduction electricity, aluminium, cement production process, and power plant's waste material flyash is the system aluminum feedstock, through fragmentation, calcining, leaching, filtration, desiliconization, the carbon operation production aluminum oxide that grades.In these patents, exist that acid concentration height, HTHP are spent carefully, used to the colliery powder abrasive particle, the aluminium yield is low and problem such as the quality product grade is low.
Through the document retrieval, do not see the public reported that adopts the low iron Tai-Ace S 150 of normal pressure acid system direct production.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of method of under condition of normal pressure, utilizing the low iron Tai-Ace S 150 of coal gangue acid system production is provided, open up new raw material resources, realize the effective high added value comprehensive utilization of coal gangue for Tai-Ace S 150 and aluminium series product.
Technical scheme of the present invention is: utilize the method for the low iron Tai-Ace S 150 of coal gangue production, its production craft step comprises:
(1) selects for use and contain Al 2O 3>25%, the coal gangue of total iron<10% is a raw material, and its broken back is required all the square hole sieve through 0.5mm;
(2) the coal gangue raw material to fragmentation carries out activation treatment, and the coal gangue raw material under 750~850 ℃, was calcined 5~10 minutes, is being cooled within 0.5~1min below 150 ℃, and grinding is to crossing 80 mesh sieve surplus<5% then;
(3) by liquid-solid mass ratio 2~4:1 batching, sulfuric acid is with measuring Al in the active coal gangue 2O 31.05~1.1 times of the theoretical acid consumption of content, rest part liquid is then with clear water or filter cake washing liquid.Stir the back and under 90~95 ℃ of temperature, react 2~4h, reacted the back filtered while hot, replace, incorporate in the filtrating with the clear water or the washing lotion that are equivalent to the filter residue quality;
(4) in step (3) gained acidleach filtrating, add coal gangue and continue reaction, service temperature is 90~95 ℃, when the pH value of solution>2.5; Slowly add oxygenant, it is constant to keep reaction conditions, when pH value>2.7 of reaction solution; Reaction terminating, filtered while hot must be hanged down the iron alum liquor;
(5) adopt vacuum concentration, step (4) gained purifying filter liquor is carried out condensing crystal, separation, drying and dehydrating, must hang down anhydrous ferric 18 Tai-Ace S 150, ferro-aluminum is than (Al 2O 3: Fe)>160, meet papermaking and the requirement of water treatment Tai-Ace S 150 technological standard top grade article.
Said acid-leaching reaction after-filtration gained bastard coal rock ballast water carries out three times and cleans; One washing lotion is used for the dosing of next acid-leaching reaction; Two washing lotions are used for the cleaning of bastard coal rock ballast behind dosing or the acid-leaching reaction of next acid-leaching reaction; Three washing lotions are used for the cleaning of bastard coal rock ballast behind the next acid-leaching reaction, and the rest may be inferred;
Said acidleach filtered liq in coal gangue neutralization, iron removal by oxidation after-filtration liquid ferro-aluminum than (Al 2O 3: Fe)>160 o'clock, reacted bastard coal rock ballast turns back to acidleach, repeats (3), (4) and (5), and iron Tai-Ace S 150 is hanged down in preparation; Ferro-aluminum in deironing liquid is than (Al 2O 3: Fe)<160 and fresh coal gangue consumption surpass 120% o'clock of acid-leaching reaction consumption for the first time, filter residue no longer recycles, reaction terminating carries out new circulating reaction again.
The used equipment of the present invention is existing known device.
After coal gangue of the present invention is activated; The aluminum oxide that exists with clay matter form changes the aluminum oxide of undefined structure into; Have good reactivity worth, with the stripping of Tai-Ace S 150 form, other soluble sulphate mainly is a molysite in the acid-respons process; Divalence and the tervalent ratio atmospheric condition during with calcining is relevant, generally speaking near 1:1.In the acidleach filtered liq, add fresh coal gangue, residual free acid at first with coal gangue in active substance react, along with the carrying out of reaction, solution PH raises gradually, as the PHZhi > of reaction solution; 2.5 the time, ferric ion begins hydrolysis, forms gel, and ferrous iron still exists in solution with ionic species, and add oxygenant this moment, and oxidation of divalent is become ferric iron, and along with the increase of reaction times and PH, the ferric iron more than 95% is converted into Fe (OH) 3And Fe 2O 3Deposition can be removed about 5% Fe (OH) through overanxious 3The gel iron rule is through the slag roasting adsorbing and removing of coal gangue, and control reaction solution pH value is no more than 3.8, in case too much Tai-Ace S 150 generation hydrolysis, said concrete reaction formula is following.
Acid-leaching reaction:
Al 2O 3+3H 2SO 4=Al 2(SO 4) 3+3H 2O
FeO+H 2SO 4=FeSO 4+H 2O
Fe 2O 3+3H 2SO 4=Fe 2(SO 4) 3+3H 2O
The deironing reaction:
Al 2O 3+3H 2SO 4=Al 2(SO 4) 3+3H 2O
Fe 3++H 2O→Fe(OH) 3?+H +
Fe 2++[O] -→Fe 3++[O] 0
2Fe(OH) 3=Fe 2O 3+3H 2O
The present invention compared with prior art has following advantage and positively effect:
1, the calcining coal gangue temperature is chosen as 750~850 ℃, satisfies the operational condition of the circulating fluidized bed that seethes with excitement, and heat is used for generating and produces steam, and plenum system is personal, and coal gangue burning slag activity is good simultaneously, no underburnt and burn-off phenomenon, the average solubility rate of aluminium>90%;
2, carry aluminium with traditional coal gangue and compare, adding assistant does not help reclaiming the coal gangue heat;
3, produce Tai-Ace S 150 with existing invention coal gangue acid system and compare, grinding is less demanding, and granularity requirements was that 80 mesh sieve screen over-sizes are 5%, and energy consumption is low;
4, need not to adopt other iron removing reagent, the aluminium loss is few, does not bring other impurity into, Al in the product 2O 3: Fe>160, satisfy the specification of quality of papermaking and water treatment Tai-Ace S 150 technological standard top grade article;
5, acid leaching, washing is countercurrent washing, recycles, and has promptly guaranteed washing effect, has reduced the loss of aluminium simultaneously;
6, acid-leaching reaction carries out under normal pressure, and reaction conditions is gentle, and acid sludge is high quality raw material of producing water glass.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
The practical implementation method
Below in conjunction with accompanying drawing and embodiment the present invention is done further elaboration, but content of the present invention is not limited to said scope.
Embodiment 1:Select for use and contain Al 2O 3>25%, the coal gangue of total iron<10% burns slag 30kg, and it is crushed to all through the 0.5mm square hole sieve, sends into fluidizing furnace; Under 750 ℃; Calcined 10 minutes, and after 0.5min, be cooled to 150 ℃ then, use the ball mill of Φ 500 * 600 to divide grinding three times again; Each grinding time is 10 minutes, must be the burning ground-slag abrasive material of 80 mesh sieve screen over-size<5%.Comprehensive appearance is through analyzing Al 2O 3, TFe content is respectively 31.57% and 6.16%.
Adopt following process step, utilize coal gangue production to hang down iron Tai-Ace S 150:
1. acidleach for the first time
Getting active coal gangue and burn slag 2000g in the there-necked flask of 1000ml, add water 4050g, put into water-bath, add 1950g concentration at last and be 98% sulfuric acid, is theoretical 1.05 times with the acid amount, and then the total liquid-solid ratio of reactant is 3:1.Temperature is 95 ℃ in the control there-necked flask, reaction times 3h, and filtered while hot is replaced with 1000ml water, incorporates in the filtrating, and with three washings of 9000ml moisture, washing lotion is stayed next time and is used.Must filtrate amounts to 6520ml, and weight 7978g is through analyzing Al in the filtrating 2O 3: Fe=5.7.
2. deironing for the first time
In above-mentioned acidleach first time filtrating, add the fresh coal gangue of 570g and burn slag, temperature of reaction is 95 ℃, and pH value is 2.6 in the time of 1.5 hours; Slowly adding concentration is 30% 17ml ydrogen peroxide 50, continues 2.5 hours afterreaction liquid pH values of reaction and reaches 3.0, filtered while hot; Replace with 570ml water; Incorporate in the filtrating, filter residue need not wash, and directly incorporates next acidleach into.Get liquid 6530ml, 7908g is through analyzing Al in the filtrating 2O 3: Fe=193.With this liquid vacuum concentrate, crystallization, drying, 18 Tai-Ace S 150 3843g, by acid-leaching reaction, yield is 93.21%.
3. acidleach for the second time
With after the filter residue oven dry of above-mentioned first time of iron removal 467g, add the fresh coal gangue of 1533g, add 1640g concentration and be 98 sulfuric acid, be Al in total coal gangue 2O 31.05 times of theoretical acid consumption, dosing amounts to 4360g, all be a washing lotion and part two washing lotions of acidleach first time last time, and reactant portion liquid-solid ratio is 3:1.Under 95 ℃ of temperature condition, carry out acid-leaching reaction 2h, filtered while hot, two washing lotions of acidleach for the first time amount to 1000ml and replace; Wash successively with remainder and three washing lotions; With the washing of 5000ml clear water, get filtered liq 6627ml, heavy 7958g, at last through analyzing Al in the filtrating 2O 3: Fe=10.7.
4. deironing for the second time
The filtrating of the above-mentioned acidleach second time is added the fresh coal gangue burning of 1100g slag, and by the method operation of deironing for the first time, temperature of reaction is 95 ℃; Continuation reaction 2 hours, reaction solution pH value reach 2.6; Add concentration again and be 30% ydrogen peroxide 50 20ml reaction 2.5h, reaction PH at the end replaces with 1100ml water 3.4; Get liquid 6317ml, heavy 8069g, through analyzing Al in the filtrating 2O 3: Fe=186.With this liquid vacuum concentrate, crystallization, drying, 18 Tai-Ace S 150 3862g, by acid-leaching reaction, yield is 93.68%.
Operation as stated above, coal gangue burns the slag consumption when progressively increasing deironing, and suitably increases the ydrogen peroxide 50 consumption, adjusts acid leaching, washing, deironing displacement clear water consumption simultaneously, and after 9 circulations, deironing coal gangue consumption has surpassed 24000g, Al in the deironing liquid 2O 3: Fe=162, by acid-leaching reaction, yield is 87.63%, and this circulation experiment stops, and carries out cyclical operation next time, and washings is then as present embodiment raw materials used next acidleach dosing and washing.
Embodiment 2:Select for use and contain Al 2O 3>25%, the coal gangue of total iron<10% burns slag 30kg, and it is crushed to all through the 0.5mm square hole sieve, sends into fluidizing furnace; Under 850 ℃; Calcined 5 minutes, and after 0.8min, be cooled to 150 ℃ then, use the ball mill of Φ 500 * 600 to divide grinding three times again; Each grinding time is 10 minutes, must be the burning ground-slag abrasive material of 80 mesh sieve screen over-size<5%.Comprehensive appearance is through analyzing Al 2O 3, TFe content is respectively 26.52. % and 9.17%.
Adopt following process step, utilize coal gangue production to hang down iron Tai-Ace S 150:
1. acidleach for the first time
Getting active coal gangue and burn slag 2000g in the there-necked flask of 10000ml, add water 6284g, put into water-bath, add 1716g concentration at last and be 98% sulfuric acid, is theoretical 1.09 times with the acid amount, and then the total liquid-solid ratio of reactant is 4:1.Temperature is 90 ℃ in the control there-necked flask, reaction times 4h, and filtered while hot is replaced with 500ml water, incorporates in the filtrating, and with three washings of 9000ml moisture, washing lotion is stayed next time and is used.Must filtrate amounts to 6715ml, and weight 7978g is through analyzing Al in the filtrating 2O 3: Fe=7.5.
2. deironing for the first time
In acidleach first time filtrating, add the fresh coal gangue of 1200g and burn slag, temperature of reaction is 90 ℃, and pH value is 2.56 in the time of 1.5 hours; Press the amount bubbling air of 20ml/min in the reaction process, continue 2.5 hours afterreaction liquid pH values of reaction and reach 3.1, filtered while hot; Replace with 500ml water; Incorporate in the filtrating, filter residue need not wash, and directly incorporates next acidleach into.Get liquid 6820ml, 7815g is through analyzing Al in the filtrating 2O 3: Fe=182.With this liquid vacuum concentrate, crystallization, drying, 18 Tai-Ace S 150 3010g, by acid-leaching reaction, yield is 86.92%.
3. acidleach for the second time
With after the oven dry of the slag of the above-mentioned deironing first time 1125g, add the fresh coal gangue of 875g, add 1250g concentration and be 98 sulfuric acid, be Al in total coal gangue 2O 31.10 times of theoretical acid consumption, dosing is that a washing lotion of acidleach last time 1 all reaches part two washing lotions, amounts to 2750g, then reactant portion liquid-solid ratio is 2:1.Under 90 ℃ of temperature condition, carry out acid-leaching reaction 2h, filtered while hot is got for the first time acid-leaching reaction two washing lotions and is amounted to 500ml and replace; Wash successively with remainder and three washing lotions; With the washing of 5000ml clear water, get filtered liq 4930ml, heavy 5154g, at last through analyzing Al in the filtrating 2O 3: Fe=17.5.
4. deironing for the second time
Filtrating in the above-mentioned acidleach second time adds the fresh coal gangue burning of 1800g slag, and by the method operation of deironing for the first time, temperature of reaction is 90 ℃; Continue reaction 2.5 hours, the reaction solution pH value reaches 2.6, and adding concentration is 30% hydrogen peroxide solution 25ml reaction 1.5h; Reaction PH at the end is 3.2; With the displacement of 500ml water, get liquid 5012ml, heavy 6223g, through analyzing Al in the filtrating 2O 3: Fe=186.With this liquid vacuum concentrate, crystallization, drying, 18 Tai-Ace S 150 2906g, by acid-leaching reaction, yield is 83.90%.
Operation as stated above, coal gangue burns the slag consumption when progressively increasing deironing, and suitably increases the hydrogen peroxide solution consumption, adjusts acid leaching, washing, deironing displacement clear water consumption simultaneously, and after 4 circulations, deironing coal gangue consumption has surpassed 24000g, Al in the deironing liquid 2O 3: Fe=163, by acid-leaching reaction, yield is 80.65%, and this circulation experiment stops, and carries out cyclical operation next time, and washings is then as present embodiment raw materials used next acidleach dosing and washing.
Embodiment 3:Select for use and contain Al 2O 3>25%, the coal gangue of total iron<10% burns slag 30kg, and it is crushed to all through the 0.5mm square hole sieve, sends into fluidizing furnace; Under 800 ℃; Calcined 8 minutes, and after 1min, be cooled to 150 ℃ then, use the ball mill of Φ 500 * 600 to divide grinding three times again; Each grinding time is 10 minutes, must be the burning ground-slag abrasive material of 80 mesh sieve screen over-size<5%.Comprehensive appearance is through analyzing Al 2O 3, TFe content is respectively 32.42% and 4.76%.
Adopt following process step, utilize coal gangue production to hang down iron Tai-Ace S 150:
1. acidleach for the first time
Getting active coal gangue and burn slag 2000g in the there-necked flask of 10000ml, add water 3940g, put into water-bath, add 2060g concentration at last and be 98% sulfuric acid, is theoretical 1.08 times with the acid amount, and then the total liquid-solid ratio of reactant is 3:1.Temperature is 93 ℃ in the control there-necked flask, reaction times 3h, and filtered while hot is replaced with 1000ml hot water, incorporates in the filtrating, and with three washings of 9000ml moisture, washing lotion is stayed next time and is used.Must filtrate amounts to 6550ml, and weight 8013g is through analyzing Al in the filtrating 2O 3: Fe=4.2.
2. deironing for the first time
In above-mentioned acidleach first time filtrating, add the fresh coal gangue of 700g and burn slag, temperature of reaction is 93 ℃, and pH value is 2.7 after 1.0 hours; Reaction process feeds the ozone amount (ozone is produced by ozonizer) of 10ml/min, continues 2.5 hours afterreaction liquid pH values of reaction and reaches 3.2, filtered while hot; Replace with 1000ml water; Incorporate in the filtrating, filter residue need not wash, and directly incorporates next acidleach into.Get liquid 7750ml, 9787g is through analyzing Al in the filtrating 2O 3: Fe=201.With this liquid vacuum concentrate, crystallization, drying, 18 Tai-Ace S 150 4118g, by acid-leaching reaction, yield is 95.00%.
3. acidleach for the second time
With after the filter residue oven dry of above-mentioned first time of iron removal 647g, add the fresh coal gangue of 1353g, add 1445g concentration and be 98 sulfuric acid, be Al in total coal gangue 2O 31.05 times of theoretical acid consumption, dosing amounts to 3555g, for the last first time of acidleach one washing lotion all with part two washing lotions, reactant portion liquid-solid ratio is 3:1.Under 93 ℃ of temperature condition, carry out acid-leaching reaction 2h, filtered while hot is got a primary washing lotion and two washing lotions and is amounted to 1000ml and replace; Wash successively with remainder and three washing lotions; With the washing of 5000ml clear water, get filtered liq 6530ml, heavy 7938g, at last through analyzing Al in the filtrating 2O 3: Fe=7.7.
4. deironing for the second time
The filtrating of the above-mentioned acidleach second time is added the fresh coal gangue burning of 850g slag, and by the method operation of deironing for the first time, temperature of reaction is 93 ℃; Continuation reaction 100 minutes, reaction solution pH value reach 2.65; Add concentration again and be 30% hydrogen peroxide solution 18ml and react 2.0 h, reaction PH at the end replaces with 1000ml water 3.4; Get liquid 6765ml, heavy 8391g, through analyzing Al in the filtrating 2O 3: Fe=196.With this liquid vacuum concentrate, crystallization, drying, 18 Tai-Ace S 150 4096g, by acid-leaching reaction, yield is 94.52%.
Operation as stated above; Coal gangue burns the slag consumption when progressively increasing deironing, and reaction process continues to feed ozone amount (ozone is produced by ozonizer) and adjusts acid leaching, washing, deironing displacement clear water consumption simultaneously, after 15 circulations; Deironing coal gangue consumption has surpassed 24000g, Al in the deironing liquid 2O 3: Fe=160, by acid-leaching reaction, yield is 84.20%, and this circulation experiment stops, and carries out cyclical operation next time, and washings is then as present embodiment raw materials used next acidleach dosing and washing.

Claims (5)

1. method of utilizing the low iron Tai-Ace S 150 of coal gangue production, it is characterized in that: be raw material with the coal gangue, get alum liquor through fragmentation, calcining, grinding, acidleach, alum liquor hangs down iron 18 Tai-Ace S 150 products through iron removal by oxidation, crystallization, dry preparation.
2. the method for utilizing the low iron Tai-Ace S 150 of coal gangue production according to claim 1, it is characterized in that: the coal gangue raw material contains Al 2O 3>25%, it is 98% sulfuric acid as concentration that total iron<10%, reaction use sour, and oxygenant is meant ydrogen peroxide 50 or ozone, air.
3. the method for utilizing the low iron Tai-Ace S 150 of coal gangue production according to claim 1 and 2 is characterized in that: concrete process step comprises:
(1) fragmentation: require all square hole sieves through 0.5mm of broken thing;
(2) thermal activation: to carrying out activation treatment through broken coal gangue raw material, activation temperature is under 750~850 ℃, and soak time is 5~10 minutes, is being cooled within 0.5~1min below 150 ℃;
(3) grinding: the activation bastard coal is carried out grinding, and it was 80 mesh sieve screen over-size<5% that the powder degree requires;
(4) acidleach: by liquid-solid mass ratio 2~4:1 batching, sulfuric acid is with measuring Al in the active coal gangue 2O 31.05~1.1 times of the theoretical acid consumption of content, rest part liquid stirs the back and under 90~95 ℃ of temperature, reacts 2~4h then with clear water or filter cake washing liquid, and filtered while hot after react uses the clear water or the washing lotion that are equivalent to the filter residue quality to replace, and incorporates in the filtrating;
(5) purify: in step (4) gained acidleach filtrating, add coal gangue and continue reaction; Service temperature is 90~95 ℃, when the pH value of solution>2.5, slowly adds oxygenant; It is constant to keep reaction conditions; When pH value>2.7 of reaction solution, reaction terminating, filtered while hot must be hanged down the iron alum liquor;
(6) concentrate drying: adopt vacuum concentration, step (5) gained purifying filter liquor is carried out condensing crystal, separation, drying and dehydrating, must hang down anhydrous ferric 18 Tai-Ace S 150, ferro-aluminum is than (Al 2O 3: Fe)>160, meet papermaking and the requirement of water treatment Tai-Ace S 150 technological standard top grade article.
4. the method for utilizing the low iron Tai-Ace S 150 of coal gangue production according to claim 3; It is characterized in that: acid-leaching reaction after-filtration gained bastard coal rock ballast divides three cleanings; One washing lotion is used for the dosing of next acid-leaching reaction; Two washing lotions are used for the cleaning of bastard coal rock ballast behind dosing or the acid-leaching reaction of next acid-leaching reaction, and three washing lotions are used for the cleaning of bastard coal rock ballast behind the next acid-leaching reaction, and the rest may be inferred.
5. the method for utilizing the low iron Tai-Ace S 150 of coal gangue production according to claim 3, it is characterized in that: ferro-aluminum is than (Al in the acid-leaching reaction filtered liq 2O 3: Fe)>160 o'clock, reacted bastard coal rock ballast turns back to acidleach, repeats (4), (5) and (6), and iron Tai-Ace S 150 crystal is hanged down in preparation; Ferro-aluminum in deironing liquid (acid-leaching reaction filtered liq) is than (Al 2O 3: Fe)<160 and fresh coal gangue consumption surpass 120% o'clock of acid-leaching reaction consumption for the first time, filter residue no longer recycles.
CN201110209467A 2011-07-26 2011-07-26 Method for producing low iron aluminum sulfate by utilization of coal gangue Pending CN102311136A (en)

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Publication number Priority date Publication date Assignee Title
CN102978389A (en) * 2012-09-28 2013-03-20 武汉工程大学 Leaching method for vanadium in vanadium-containing stone coal
CN103121701A (en) * 2013-03-18 2013-05-29 昆明理工大学 Method for preparing non-iron aluminium sulfate by using coal gangue cinders
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CN105523561A (en) * 2016-01-19 2016-04-27 内蒙古日盛可再生资源有限公司 Method for efficiently desilicating high alumina coal gangue
CN106830240A (en) * 2017-01-10 2017-06-13 太原理工大学 A kind of method of utilization bastard coal ground mass flocculant process black water
CN109384252A (en) * 2017-08-09 2019-02-26 抚顺市盛达工业产品综合利用有限公司 Coal measures association tailing produces aluminium technique
CN109234527A (en) * 2017-09-14 2019-01-18 太原理工大学 A kind of super (Asia) critical activation method and its application of gangue
CN108862342A (en) * 2018-08-08 2018-11-23 山西载驰科技有限公司 A kind of modified gangue preparation γ-Al2O3The method of nanometer sheet

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