CN109928472A

CN109928472A - By the method for aluminium ash, the water purification agent of sulfuric acid and the preparation of optional red mud containing polyaluminium sulfate

Info

Publication number: CN109928472A
Application number: CN201910161861.0A
Authority: CN
Inventors: 焦占忠; 张凤炳; 赵刚; 谷桂芝; 韩纪磊; 杨保鑫; 焦文帅
Original assignee: Shandong Aluminum Hui Environmental Protection Technology Co Ltd
Current assignee: Shandong Aluminum Hui Environmental Protection Technology Co Ltd
Priority date: 2019-03-04
Filing date: 2019-03-04
Publication date: 2019-06-25

Abstract

The present invention provides a kind of method by aluminium ash, the water purification agent of sulfuric acid and the preparation of optional red mud containing polyaluminium sulfate, the following steps are included: by aluminium ash, with sodium carbonate and/or sodium hydroxide, calcic raw material, it mixes, it is roasted at 400-1000 DEG C of oxidizing atmosphere, roasting generates material and reacts with sulfuric acid and optional red mud, until slurries filtrate pH3.0-4.0, Al₂O₃5-12m%, basicity 40-75, filtering, filtrate are the water purification agent containing polyaluminium sulfate, and filter residue washing gained solid slag is further utilized or stored up, fills.By mixing calcination steps disposably solve the problems, such as the prior art need the metallic aluminium that could be handled by two steps or three steps hydrolyze or inflammable and explosive, the aluminium nitride acidolysis of acidolysis hydrogen release gas produce ammonium enter purified caused by water purification agent after water ammonium nitrogen problem, fluorine-containing stabilisation, innoxious problem with activation problem and the aluminium ash of low activity aluminium oxide especially Alpha-alumina；In water purification agent product use process, the hardness increase of treated water is smaller.

Description

Water purification agent containing polyaluminium sulfate is prepared by aluminium ash, sulfuric acid and optional red mud Method

Technical field

The invention belongs to nonferrous metallurgy environmental technology fields, and in particular to a kind of by aluminium ash, sulfuric acid and optional red mud system The method of the standby water purification agent containing polyaluminium sulfate.

Background technique

Aluminium ash is the important solid waste of aluminum i ndustry, according to source and the difference of metal aluminum content, is generally divided into primary Aluminium ash and Quadratic aluminum dust；In addition to containing metallic aluminium, aluminium ash generally goes back sodium chloride-containing, potassium chloride, fluoride salt, aluminium oxide, aluminium nitride.One The metal aluminum content of secondary aluminium ash is higher, usually through such as the methods of salt bath processing recycling metallic aluminium.Quadratic aluminum dust includes by a secondary aluminium Residue after ash recycling metallic aluminium, metal aluminum content is lower than secondary aluminium ash；Quadratic aluminum dust, which can also unite, refers to that no metallic aluminium returns The aluminium ash of value is received, metallic aluminium, which may be up to 20%, aluminium nitride, in component and content may be up to 30%, the general 20-50% of aluminium oxide. Quadratic aluminum dust complicated component, impurity is more, is not easy by simply purifying or processing returns to utilizations.

Aluminium ash includes contained metallic aluminium, aluminium nitride in Quadratic aluminum dust, and content is higher, surface area is larger, property is relatively living It sprinkles, hydrolyzable generates hydrogen when metallic aluminium contained therein meets water or the moisture absorption, measures big Shi Youyi and fires danger, contained aluminium nitride meets water Or hydrolyzable generates ammonia or forms ammonia nitrogen when the moisture absorption, causes stench；Contained fluoride salt such as NaF, KF is water-soluble, Qi Taru AlF₃、Na₃AlF₆Although solubility is very low in water, it is dissolved out still above environmentally friendly limit value, easily causes the fluorine of water body and soil Pollution, institute's sodium chloride-containing, potassium chloride etc. easily dissolve out, and can cause water body and soil salinity characters, thus aluminium ash is included into National Hazard The hazardous waste of waste register 2016, existing discharge per ton collects 1000 yuan of environment protection tax, and needs to pay and fill including stockpiling Land occupation, construction, aluminium ash transport stockpiling landfill, maintenance control etc. expenses, also to undertake may generation risk of environmental pollution and Processing cost.

Before, aluminium scrap ash includes that Quadratic aluminum dust is stacked or filled mostly, and utilization is less, at present due to legislations of environmental protection The implementation with environmentally friendly tax is implemented, has motive force largely to be utilized.Since alumina content is higher, aluminium scrap ash includes Quadratic aluminum dust A kind of purposes be to prepare aluminium chloride or aluminium polychloride, including solution or solid product.

In the prior art, include Quadratic aluminum dust as silicon source by aluminium scrap ash and prepare the solution of chloride containing aluminium or containing polyaluminium The method of aluminum solutions, generally includes following steps: (1) water soluble salts such as sodium chloride, potassium chloride adding water to dissolve and recycling；(2) Aluminium nitride is hydrolyzed in such as 80-100 DEG C or so water, generates aluminium hydroxide and ammonia, and ammonium hydroxide benefit is made through water absorption in ammonia evolution With or outside sell, part metals aluminium also hydrolyze generation aluminium hydroxide and hydrogen in step processing；(3) add the hydrolysis of dissolving with hydrochloric acid end again Metallic aluminium, newly-generated aluminium hydroxide and amount of activated higher aluminium oxide are separated by solid-liquid separation after reaction and obtain containing AlCl₃Solution Or polymeric aluminum chlorides solution, the latter obtain when the amount of added hydrochloric acid is less, the very low aluminium oxide of the activity of end reaction is especially Alpha-alumina and other insoluble components such as calcirm-fluoride, aluminum fluoride, ice crystal, silicate enter solid slag；(4) solid slag is with enough It is roasted after calcium oxide or calcium carbonate such as agstone at such as 1200-1400 DEG C, key reaction is to generate calcium aluminate, and aluminium oxide is living Change, villiaumite is converted into calcirm-fluoride and reaches solid fluorine purpose, product of roasting can with hydrochloric acid, liquor alumini chloridi, or with hydrochloric acid, aluminium chloride Mixed solution reaction, prepares the solution of chloride containing aluminium or the solution containing aluminium polychloride, is separated by solid-liquid separation gained chloride containing aluminum solutions Or the solution containing aluminium polychloride, when the indexs such as fluorine, heavy metal meet the requirements, it can be used as water purification agent product.

Also having first includes that Quadratic aluminum dust directly adds hydrochloric acid to react by aluminium scrap ash, because of exothermic heat of reaction, temperature rise can reach 70 DEG C with On, sodium chloride, potassium chloride enter solution, and metallic aluminium generates aluminium chloride and hydrogen, and aluminium nitride dissolution generates aluminium chloride and ammonium chloride, It is separated by solid-liquid separation and is obtained containing AlCl after reaction₃Solution or solution and solid slag containing aluminium polychloride, polymeric aluminum chlorides solution is in institute It is obtained when adding the amount of hydrochloric acid less；The villiaumite for being insoluble or poorly soluble in water is converted into if containing water-soluble villiaumite such as NaF, KF as being fluorinated Aluminium, cryolite, potassium fluoroaluminate, could generate that solubility is extremely low, does not easily cause the calcirm-fluoride of fluoride pollution in raw material when calcic, but Also only contain or be added it is enough fluorine can be completely converted into calcirm-fluoride when could consolidate fluorine, it is sometimes desirable to prolonged reaction turns Fluorine could be completely converted into calcirm-fluoride by change, solve the pollution problem of fluorine in aluminium ash；The solution of gained chloride containing aluminium contains polymerization The solution of aluminium chloride, sodium chloride-containing, potassium chloride, ammonium chloride, solid slag main component are that the very low aluminium oxide of the activity of end reaction is outstanding It is Alpha-alumina and other insoluble components such as calcirm-fluoride, aluminum fluoride, ice crystal, silicate, at above-mentioned steps (4) Reason and preparation, reach the purpose and obtain the product.After step (4) solid slag matches enough calcium oxide or Paris white It is roasted at such as 1200-1400 DEG C, aluminum oxide activating generates the roasting material of calcium aluminate, if being changed to hydrochloric acid used as 20-35m% is dense The dilute sulfuric acid of degree can also prepare the water purification agent containing polyaluminium sulfate, but be incorporated calcium oxide or calcium carbonate are converted mainly into sulfuric acid Calcium enters solid slag, causes solid slag quantum of output excessive, while reducing the utility value of solid slag, and produces the heap of a large amount of solid wastes It deposits, transportation problem.

The prior art includes Quadratic aluminum dust as alumina source preparation by aluminium scrap ash and contains polyaluminium chloride water purification agent, contains The method of polyaluminum sulfate aluminium water purifying agent, major defect are:

1, contained metallic aluminium hydrolyzes or reacts output hydrogen with hydrochloric acid, then more demanding to the burn-proof and explosion prevention condition of equipment, is opening Sometimes it can see the burning of hydrogen in mouthful reaction tank, the also frequent generation explosive sound of some is also less prone to there are security risk using making The lower glass reinforced plastic reaction vessel of valence or the reaction tank for serving as a contrast glass fibre reinforced plastic coating；Some aluminium ash in also contain a small amount of cyanogen, and salt The initial stage of acid reaction, mid-term may release and poison great hydrogen cyanide gas, cause a hidden trouble to health, the safety of operator, When into water purification agent product, may cause it is net after water cyanogen content it is exceeded；

If 2, contained aluminium nitride hydrolyzes output ammonia, ammonium hydroxide, need purposes or can sell, influences water purification agent if stifled library Production, prepares ammonium chloride with absorption by Hydrochloric Acid and then needs equipment investment and running expense；Contained aluminium nitride and hydrochloric acid reaction generate chlorine Change ammonium to be then not readily separated, causes ammonium nitrogen problem into water purification agent, limit the purposes of polyaluminium chloride water purification agent；

3, after washing or pickling filter residue with calcium oxide, calcium carbonate activated alumina roasting generally using 1200-1400 DEG C compared with High-temperature, equipment manufacturing cost and energy consumption are high；

4, prior art usually requires two slurry reaction processes, two filter and cleaning process and a wet feed high-temperature roasting work Sequence, two of them filter and cleaning process, filter residue contain superfine solids, and hardly possible is cleaned, and diafiltration is all relatively slow more difficult, consume fresh water compared with More, efficiency is lower, need to use the higher leaf filter of pressure or sheet frame filter, can not be using diafiltration is high-efficient, speed is fast, it is new to consume Fresh water is more manually to occupy that less, labor intensity is low, the lower vacuum band-type filter machine of operating cost；It is thinner when filter residue water drenching Part, which is easy to run off, causes environmental pollution；

5, integrated artistic is complex, and operating cost is higher, and equipment investment is high, and occupied ground, plant area are big.

Summary of the invention

In order to solve the above technical problems, the present invention provides a kind of, sulfuric acid preparation water purification agent containing polyaluminium sulfate grey by aluminium Method, comprising the following steps:

A. by aluminium ash, with one or both of the desired amount of sodium carbonate, sodium hydroxide, the desired amount of calcium carbonate, calcium oxide, grass One of sour calcium, calcium citrate, calcium sulfate are a variety of, mix, and roast at 400-1000 DEG C of oxidizing atmosphere, and roasting is made and generates Material；

B. roasting is taken to generate material, with sulfuric acid and optional water source, reaction prepares slurries, it reacts to slurries filtrate pH3.0-4.0, Al₂O₃5-12m%, basicity 40-75；

C. step B slurries filter, and filtrate is the water purification agent containing polyaluminium sulfate, and filter residue washing gained solid slag further utilizes or heap It deposits, fill；

Wherein, the fluorine-containing calcirm-fluoride that is converted into of calcium contained by calcic raw material described in step A and aluminium ash institute deducts calcic institute, aluminium ash institute The calcium needed, amount ratio are (1.5-10): 1.

The process characteristic of the method for the present invention is in 400-1000 DEG C of roasting process of oxidizing atmosphere of step A, using being matched Metallic aluminium contained by aluminium ash is oxidized to aluminium oxide by the oxygen in air or atmosphere, is aluminium oxide and nitrogen by contained oxidized aluminum nitride Gas, by it is contained with the very low aluminium oxide of sulfuric acid reaction activity especially at least part of Alpha-alumina and be incorporated sodium carbonate, The sodium aluminate or sodium metaaluminate that sodium hydroxide reaction generates facile hydrolysis, easily reacts with acid, to make aluminum oxide activating contained by aluminium ash； One of the be incorporated calcic raw material, that is, calcium carbonate, calcium oxide, calcium oxalate, calcium citrate, calcium chloride or a variety of and aluminium Grey institute's calcic, and aluminium ash institute is fluorine-containing generates stable calcirm-fluoride, the speed of generation calcirm-fluoride under the conditions of high-temperature roasting of the present invention Comparatively fast, degree is more complete, and generated calcirm-fluoride is more stable, in the generation of the polymer such as the acid processing of step B and polyaluminium sulfate Process dissolves out or carries secretly less, and fluorine content is lower in the filtrate of step C or water purification agent product.Wherein step A is disposably solved The prior art needs the inflammable and explosive problem of the metallic aluminium that could be handled by two steps or three steps hydrolysis or acidolysis hydrogen release gas, nitridation The ammonia of aluminum water solution utilizes, aluminium nitride acidolysis produces ammonium and enters water ammonium nitrogen problem and low activity oxidation after purification caused by water purification agent The fluorine-containing stabilisation of activation problem and aluminium ash, the innoxious problem of aluminium especially Alpha-alumina, technique simplify, investment and Running expense is all lower.The filter residue usually belongs to general solid waste, and further application, discharge or stockpiling are limited less, does not also deposit In environment protection tax problem.Aluminium ash of the present invention includes by remaining Quadratic aluminum dust after secondary aluminium ash recycling metallic aluminium and not having The aluminium ash of metallic aluminium recovery value.Although another it is noted that fluorine-containing simultaneously, calcic in some aluminium ash, since fluorine, calcium match Etc. reasons, calcium fluoride containing or most of fluorine do not exist in the form other than calcirm-fluoride, these fluorine, calcium, in the strong of the method for the present invention Relatively more stable calcirm-fluoride can be converted under alkaline hot conditions.

The method of the present invention using sodium carbonate and/or sodium hydroxide as aluminium ash roasting ingredient, be eventually converted into sodium sulphate into Enter water purification agent product；Compared with calcium carbonate, calcium oxide low with the fusing point of sodium carbonate and/or sodium hydroxide, alkalinity is strong, lower Maturing temperature under the conditions of can be realized by aluminium ash contained by metallic aluminium be oxidized to aluminium oxide, by contained oxidized aluminum nitride be aluminium oxide And nitrogen, by the contained aluminium oxide very low with dilute sulfuric acid reactivity especially Alpha-alumina generate facile hydrolysis, easily with acid react Sodium aluminate or sodium metaaluminate, while realizing and being converted into aluminium ash institute is fluorine-containing stabilization with added calcic raw material, be not easy subsequent Multiple purposes such as the calcirm-fluoride dissolved out in reaction process roast ingredient as aluminium ash according to a large amount of calcium carbonate and/or calcium oxide, Then maturing temperature is usually required at 800-1200 DEG C.

In the step A, metallic aluminium oxidation, oxidized aluminum nitride, sodium carbonate, sodium hydroxide with by metallic aluminium, nitridation alumina Metaplasia is relatively easy at the reaction of aluminium oxide, and speed is all very fast；Activity very low aluminium oxide especially Alpha-alumina and sodium carbonate, The reaction of sodium hydroxide is slower, is the key that roasting process.Remained in roasting raw material of the invention aluminium ash contained by sodium chloride, The fusing points such as the calcirm-fluoride generated in potassium chloride, sodium fluoride, potassium fluoride, aluminum fluoride, ice crystal, calcirm-fluoride and roasting process are remote Lower than the ingredient of aluminium oxide, mixture fusing point of these ingredients in the electrolysis of metallic aluminium, casting, founding and process is usual Only 1000 DEG C or so, especially in conjunction with sodium carbonate/sodium hydroxide, after consolute, rush can be played in the roasting process of step A Into the sintering aids role reacted between aluminium oxide, sodium carbonate, sodium hydroxide, wherein sodium fluoride, potassium fluoride, aluminum fluoride, ice crystal be gradually It is converted into more stable calcirm-fluoride.The fast speed of step C filtration washing, filter residue easily clean, consume fresh water it is less, efficiency compared with Height, main cause may be that roasting generation material granularity is moderate, and the contained sodium chloride, potassium chloride, calcirm-fluoride help burning in powder Ingredient has and is greatly dispersed between sodium aluminate/sodium metaaluminate, remaining aluminium oxide microparticle, plays cementation, will Powder bonding is got up, and makes it have special skeleton structure and intensity appropriate, and the skeleton structure of powder and intensity are in step It is largely kept during the slurry reaction of rapid B or after reaction, especially significant destruction and reduction, reason occur for end It is that generated larger amount of calcirm-fluoride is not involved in reaction in slurry reaction and is all retained, thus slurries are easily filtered, filter residue It is easy to wash, it can be used and manually occupy that less, labor intensity is low, continuous production, the lower vacuum band-type filter machine of operating cost.This Invention it has also been found that by the introduced cyanogen of aluminium ash can in the oxidizing atmosphere high-temperature alkaline roasting process of step A it is completely cleared.

In step A, aluminium ash with the sodium carbonate/sodium hydroxide, calcic raw material, can grind in the ball mill, mix, send out The dust being now not present fires risk because due to containing metallic aluminium is that may be present.Aluminium ash acid adding is kept contained metallic aluminium molten by the prior art It solves, stint the reason for overcoming the problems, such as or tolerating that institute's hydrogen producing fires, allowing for contained less low metal aluminum content makes The risk that aluminium ash may explode during dry ball milling.As that can be found in handbook, 45 microns, 0.1 micron metal aluminium powder Aerial lower explosion limit is 65g/m respectively³、50g/m³, blast characteristics are respectively 1 grade (faint or medium explosion), 2 grades (big Code explosion), the aluminum dust blast accident that the country also once repeatedly produced serious casualties in recent years.But the present invention is to representative aluminium Ash has carried out the research of the blast characteristics in air with powder after lime stone/calcium oxide mill, and discovery belongs to 0 grade (not exploding), main former Because may is that, institute's saliferous has promoted gradually refinement, the effect of dispersed metal aluminium during dry ball milling in aluminium ash, makes it Largely surface oxidation occurs, to reduce its activity, and the resistance of a large amount of aluminium oxide, calcium carbonate/calcium oxide, salt Every, package and endothermic effect, avoid the burning of its dust cloud and be further likely to occur explosion.Since dry ball milling needs Flour dust overflow is controlled, the rate of air circulation inside and outside ball-grinding machine is smaller, in aluminium ash and lime stone/calcium oxide mixture ball milling mistake Cheng Zhong, in ball mill air institute it is oxygenous have largely to gradually use up reduced with content, thus aluminium ash in mechanical milling process Fire that there is very little risk with lime stone/calcium oxide mixture.

In step A, it can be (0.4-1.0) using when sodium hydroxide with the mass ratio of aluminium ash: 1, preferably (0.5- 0.8): 1.Calcic raw material institute's calcic and aluminium ash institute it is fluorine-containing be converted into calcirm-fluoride deduction aluminium ash institute calcic needed for calcium, amount Than for (1.5-10): 1, preferably (3-7): 1.

In step A, 500-800 DEG C of the maturing temperature preferably, it can be achieved that the conversion of the complete oxidation of metallic aluminium and aluminium nitride, The relatively overactivity rate of low activity aluminium oxide, fluorine are completely converted into calcirm-fluoride, and calcining time 1-3 hours, energy consumption was moderate.Roasting Rotary kiln can be used in equipment, and input and output material is powder；Tunnel oven can also be used, in addition to the kiln furnitures such as material loading saggar will be direct after mixing Roasting can also roast material after mixing by the modes dry-press process such as briquetting, pelletizing, then into tunnel oven or shaft kiln.

In step A, the oxidizing atmosphere is formed by air-supplied or oxygen-enriched air, preferably by feeding dehydration or dehumidifying Air or oxygen-enriched air formed.When usual air because moisture content (20 DEG C of water saturation vapour pressure, 2.3kPa；30 DEG C, 4.2kPa； 40 DEG C, 7.3kPa), still there is hydrolysis of aluminium nitride to release ammonia and cause roaster tail gas excessive problem containing ammonia, the reason is that in roaster Hydrolysis of aluminium nitride rate is accelerated when the neutralization of material temperature-rise period reaches maximum temperature, and released ammonia can not be fully oxidized to nitrogen Gas, especially cold stage hydrolysis of aluminium nitride release ammonia substantially cannot or only small part is oxidized to tasteless nitrogen.Step A Material is during tunnel oven calcination process after the mixing, and when feeding dehumidified air or oxygen-enriched air, end finds that arranged tail gas has Ammonia odor, but when feeding last dehumidified air, it is found that arranged tail gas has ammonia odor.Benefit using oxygen-enriched air includes its preparation It has dehumidified in the process, slightly lower roasting furnace temperature can be used to reduce roasting energy consumption.It is hot for matching burning in air furnace with natural gas The kiln interior air-flow moisture content in source is higher, and in the higher aluminium ash ingredient of processing nitridation aluminium content, tail gas need to lead to containing ammonia Cross the processing of solution absorption plant.

Step B roasting generates material with sulfuric acid, water reaction process, is guaranteeing not generating excessive vapor and other volatile matters Under the premise of, slurry temperature can be the temperature from room temperature to slightly below slurries boiling point；Since exothermic heat of reaction amount is very big, slurries temperature Degree rises comparatively fast, and initial reaction stage is mainly to control the volatilization of hydrogen chloride, and the reaction middle and later periods is mainly the volatilization of water；Generally pass through control Charging rate processed controls temperature, or by keeping boiling reaction state byproduct steam to be used for the preheating of other low temperature feed liquids, Exothermic heat of reaction control slurry temperature can be removed by modes such as cooling water coil, collets；Faster add can also be used in the reaction later period Expect speed, exothermic heat of reaction is evaporated with moisture to be removed, and slurries can achieve or be slightly below its boiling temperature at this time.Step B passes through control System roasting generates the basicity of the input amount control slurries filtrate into slurries of material.

In step B in reaction process, the citric acid, calcium citrate or sodium citrate of 0.1-0.5m% can also be added, as The stabilizer of the prepared product of aluminium water purifying agent containing polyaluminum sulfate, to improve stabilization of the water purification agent product in storage and use process Property.

Step C filtrate can further prepare solid-state water purification agent by heat dehydration, using spray drying or rotating cylinder when heat dehydration Drying mode and equipment.

It may be incorporated into iron in step B slurries, prepare polymeric aluminum sulfate iron composite water purifying agent.The mode for introducing iron includes adding Enter ferric sulfate or its solution or sulfuric acid sulfur acid iron used, can also be added by Bayer process red mud or Iron Ore Powder and sulfuric acid reaction The sulfur acid iron slurries of generation or sulfuric acid used, which are first reacted with Bayer process red mud or Iron Ore Powder, generates ferric sulfate, for example reaction is held After sulfuric acid is added in device, first plus Bayer process red mud or Iron Ore Powder react to the meltage of iron and reach requirement, then are initially added into described Roasting generates material, and the reaction was continued, ultimately generates the composite water purifying agent containing polymeric aluminum sulfate iron, using can also be when ferrum sulfuricum oxydatum solutum It is gradually added into during slurries pH2-4.0；Ferrous sulfate or its solution can also be added or sulfuric acid sulfur acid used is ferrous, or be added It is sub- that the solution or sulfuric acid used of the sulfur acid ferrous iron generated by waste iron filing and sulfuric acid reaction first add waste iron filing reaction to generate sulfuric acid Iron, until ferrous meltage reaches requirement, and especially in the slurries pH2-4.0 phase in the reaction process for preparing slurries Between blast air, oxygen-enriched air, oxygen, or hydrogen peroxide solution, liquor natrii hypochloritis, calcium hypochlorite solution is added, is polymerizeing Handle during the generation reaction of aluminium iron sulfate by ferrous oxidising as ferric iron, ultimately generate containing polymeric aluminum sulfate iron it is compound only Aqua can also be gradually added into using when ferrous sulfate solution during slurries pH2-4.0；A kind of available ferrous sulfate source is Ilmenite-sulfuric acid method titanium pigment process units ferrous sulfate by-product, ferrous sulfate heptahydrate content 90% or so.It is described containing poly- Close Fe in composite water purifying agent, that is, slurries filtrate of aluminium iron sulfate₂O₃Effect is preferable when 1-3.5m%.

Step C filter residue fresh water wash washes out contained most of water purification agent ingredient, and washing rear solid slag can reach further Using or stockpiling, landfill quality requirement；Cleaning solution go step B prepared as diluting concentrated sulfuric acid sulfur acid aqueous solution water Source, while water purification agent ingredient contained by filter cake being recycled, eventually enter into water purification agent product.The main component packet of solid slag obtained by step C The inert alumina and calcirm-fluoride and a small amount of calcium sulfate, the filter residue for including end activation can belong to general solid waste, due to containing it is more can As sintering aid, the calcirm-fluoride of mineralizer, the raw material or ingredient for being suitable for use as sintering building materials, being sintered cement can reduce its burning Junction temperature, and improve its product quality.In the sintered material of some cement include fluorite, 3000 yuan or so one of recent price Ton, the expense of raw materials of fluorite can be reduced using solid slag of the present invention.In the method for the present invention, aluminium ash raw material institute is fluorine-containing, all to be fluorinated Calcium form enters filter residue；The solubility product of calcirm-fluoride is (3.5-4) × 10^-11, far below (6.5-7) of common villiaumite such as magnesium fluoride ×10^-9, step C filtrate is that fluorinated volume is especially low in water purification agent product of the present invention.

In the composite water purifying agent of prepared water purification agent or polymeric aluminum sulfate iron containing polyaluminium sulfate, contain contained by aluminium ash Whole sodium chloride, the water soluble salts such as potassium chloride, the sodium carbonate and/or sodium hydroxide of step A supplying ultimately generate sodium sulphate into Enter product, play the role of electrolyte in the application of water purification agent, in water purification process flocculation, sedimentation have positive effect and Positive effect.

Sulfuric acid used in the present invention can be in addition to absorb preparation by troilite, sulfur burning, oxidation, water synthesizes sulfuric acid Using certain by-product sulfuric acid, Waste Sulfuric Acid, if its without influence the prepared water purification agent containing polyaluminium sulfate of the method for the present invention and The quality of produced solid slag especially objectionable impurities content or contained nocuousness it is miscellaneous to the prepared water purification agent containing polyaluminium sulfate and The quality of produced solid slag does not impact, and cannot contain exceeded organic matter；For example, metal less containing organic principle can be used The less fluorine-containing Waste Sulfuric Acid of impurity, contained HF can in the slurry reaction of step B with the roasting powder contained by together with fluorine, and Ca²⁺Reaction generates CaF₂Into solid slag；, iron aluminium less containing organic principle can be used when preparing polymeric aluminum sulfate iron composite water purifying agent The less iron content Waste Sulfuric Acid of metal impurities or Waste Sulfuric Acid containing aluminium in addition.In the available Waste Sulfuric Acid, the country of fluorine-containing Waste Sulfuric Acid For annual output at 3,000,000 tons or more, iron content Waste Sulfuric Acid is mostly derived from pickling iron and steel, and domestic annual output is more.Recent 98% industrial sulphur 90% Waste Sulfuric Acid price of 300-500 yuan/ton of acid value lattice, the hydrogen fluoride containing 0.5-2% is often -100 yuan/ton.Using containing hydrogen fluoride Waste Sulfuric Acid when, the introduced hydrogen fluoride of Waste Sulfuric Acid also should by generate calcirm-fluoride remove, in addition to using roast generate material contained by Calcium carbonate, calcium oxide, calcium chloride can also be added in calcium into slurries.

Since the discharge of aluminium ash is there are 1000 member ring per ton is bonded, real price is equivalent to -1000 yuan/ton；Side of the present invention Method can not pursue the utilization rate of aluminium oxide in aluminium ash, and pursue treating capacity.Thus, the method for the present invention step A can using compared with Low maturing temperature, equipment manufacturing cost and energy consumption are reduced, while the calcirm-fluoride in produced solid slag is burnt for cement, building materials When knot it is with higher activity and help burning effect.

In step B, Bayer process red mud used in the slurries of sulfur acid iron first is generated with sulfuric acid reaction to introduce iron oxide, is The impurity such as iron, titanium, fluorine when bauxite is leached through highly basic in Bayer process aluminum oxide production process in bauxite and the overwhelming majority The residual residue that silicon is insoluble and is formed, Fe₂O₃20% or more content.Because containing the more clean water-soluble sodium aluminate in end and can be slow The ingredient such as sodium nepheline of alkali is dissolved out, red mud is in stronger alkalinity, has pollution to water body and soil, its current environment protection tax is 25 yuan/ton.Bayer process red mud less the reason of being directly used in cement, building materials mainly its alkalinity and alkali content.The present invention passes through Water-soluble sodium aluminate in added Bayer process red mud is all dissolved out, a part of iron oxide is dissolved out, by small part by sulfuric acid to leach Aluminium oxide, the alkali that can slowly dissolve out largely dissolve out, and eventually enter into water purification agent product.Bayer process red mud can be the method for the present invention Major part contained by water purification agent or even whole iron oxide and small part aluminium oxide, water soluble salt be provided, the molten red mud slag of end acid into Enter filter residue and washing gained solid slag；Since the sodium aluminate in contained alkali, easily washed out all dissolves out, the alkali that can slowly dissolve out is most of Dissolution, institute is fluorine-containing to be cured as calcirm-fluoride, to the influence very little of water body and soil, thus in step B reaction vessel after addition sulfuric acid, First plus Bayer process red mud reacts to the meltage of iron and reaches requirement, or has added Bayer process red mud and reacted to the meltage of iron The sulfuric acid slurries for reaching requirement, in addition to that can prepare the composite water purifying agent containing polymeric aluminum sulfate iron, filter residue washing gained solid slag can For the ingredient of cement, building materials, or as Ordinary solid waste stockpiling, landfill.

It also found that the solution of sulfur acid aluminium obtained by the method for the present invention or the solution fluorinated volume containing polyaluminium sulfate are lower, far It directly reacts, then plus is added obtained by sodium carbonate or sodium hydroxide high-temperature roasting mainly containing aluminic acid by its filter residue with dilute sulfuric acid lower than aluminium ash The solution of sulfur acid aluminium prepared by solid slag or the solution containing polyaluminium sulfate are separated after the roasting material reaction of sodium, after reason should be Conversion of some fluorides contained by aluminium ash raw material to calcirm-fluoride may be relatively slow in person's reaction, or generated calcirm-fluoride is easily entrained in In polyaluminium sulfate micelle, or it is not easy to filter only because particle is subtle, but fluorine whole energy under the strong basicity hot conditions of the method for the present invention It is converted into relatively more stable calcirm-fluoride, and is difficult to dissolve out in dilution heat of sulfuric acid, is not easy to be entrained in polyaluminium sulfate micelle In, slightly easily filter is net for particle.

In conclusion method of the present invention by aluminium ash, sulfuric acid and the preparation of optional the red mud aluminium water purifying agent containing polyaluminum sulfate, Major advantage is:

1, metallic aluminium hydrolysis or acid contained by the aluminium ash that the prior art needs to handle by two steps or three steps are disposably solved The inflammable and explosive problem of hydrogen is liberated, the Peculiar Smell of the produced ammonia of hydrolysis of aluminium nitride, aluminium nitride acidolysis produce ammonium and enter water purification agent Caused by purify after water ammonium nitrogen problem and the activation problem of low activity aluminium oxide especially Alpha-alumina；

2, lower, the security risks such as no hydrogen combustion explosion, ammonia leakage are required to the burn-proof and explosion prevention condition of slurry reaction equipment, The lower glass reinforced plastic reaction vessel of cost also can be used or serve as a contrast the reaction tank of glass fibre reinforced plastic coating；

3, some aluminium ash in contained a small amount of cyanogen, in oxidizing atmosphere high-temperature calcination process oxygenolysis remove and it is innoxious, make Roasting generate material with the initial stage of sulfuric acid reaction, mid-term, the great hydrogen cyanide gas of nonhazardous releases, is not good for operator Health, safety cause a hidden trouble, and do not enter water purification agent product, do not cause the cyanogen content of water after purifying exceeded；Aluminium used in the method for the present invention Grey raw material does not include the aluminium ash containing poisonous and harmful elements such as vanadium；

4, aluminium ash in institute it is fluorine-containing entered in the filter residue i.e. solid slag of the method for the present invention with being fluorinated calcium form, produced solid slag for generally consolidate It is useless；Even if prepared water purification agent product carries minimal amount of calcirm-fluoride secretly, the quality and using effect of water purification agent product are nor affected on； Reason is that the solubility product of calcirm-fluoride is (3-4) × 10^-11, solubility is minimum in almost common fluoride, in water, dilute Solubility in acid is especially low, and by more stable after high-temperature roasting, dissolution is slower；It is easy to run off when water drenching contained by filter residue relatively thin Calcirm-fluoride it is less, stockpiling landfill when be not easy to be taken out of by water drenching and caused environmental pollution；

5, the fast speed of step C filtration washing, filter residue are easily cleaned, and consumption fresh water is less, and efficiency is higher, can be used and manually accounts for With less, labor intensity is low, continuous operation, the lower vacuum band-type filter machine of operating cost；

6, the method for the present invention, integrated artistic more simplify, and operating cost is lower, and equipment investment is low, occupied ground, plant area It is small；

7, water purification agent product prepared by the method for the present invention, in addition to containing polyaluminium sulfate, the also sodium sulphate containing higher concentration, chlorination Sodium, potassium chloride play the role of electrolyte in the application as water purification agent, have product to flocculation, the sedimentation in water purification process Pole effect and positive effect；After iron-bearing material is added in preparation process, composite polymeric aluminium iron sulfate generated, as net There is better effect in the application of aqua, have both the excellent results of polyaluminum sulfate aluminium water purifying agent, polymerization iron sulfate water-purifying agent, it can Big and closely knit, easily settled alumen ustum and sediment are formed, drops that turbid effect is good, trivalent iron salt has certain oxidability, can break The molecular structure of bad some small algae is simultaneously aggregated it quickly, while having one to be set for the oxidation, removal and agglutination of organic matter With the turbid purification of drop especially suitable for high muddy water；Inhibited by contained a large amount of sodium sulphate, water purification agent product calcium content is extremely low, makes With in the process, the calcium concentration of treated water does not increase；

8, the method for the present invention can consume for example fluorine-containing Waste Sulfuric Acid of a large amount of Waste Sulfuric Acids, iron content Waste Sulfuric Acid or Waste Sulfuric Acid containing aluminium and aluminium work Industry waste such as aluminium ash, red mud, there is higher environmental benefit.

Specific embodiment

Technical solution of the present invention is specifically described and is illustrated below with reference to embodiment, but is not constituted to of the invention Limitation.

Embodiment 1

The water purification agent containing polyaluminium sulfate is prepared as follows:

A. certain Quadratic aluminum dust M1000kg(-10 mesh is taken, 1) chemical component is shown in Table to be put into sodium hydroxide 550kg, calcium oxide 65kg Ball mill, mixing and ball milling 5hr is to -80 mesh, and powder is made roasting and gives birth in 500 DEG C of roasting 3hr of minitunnel kiln air atmosphere after mill At material；

B. in 5000L reaction tank, add tap water 2700L, open stirring, add 98m% industrial sulphuric acid 875kg, gradually put into slightly warm The roasting of degree generates material and reacts, 85-90 DEG C of temperature control after slurries are gradually heated to 85 DEG C, and roasting is suitably reduced before overtemperature and generates material Feed temperature and charging rate, reaction time 1.5hr, until slurries filtrate pH3.8, Al₂O₃6.3m%, basicity 51；

C. step B slurries are filtered through leaf filter, and filtrate is the liquid water purification agent containing polyaluminium sulfate；Filter residue tap water 1500L Washing, final outflow water pH6, washing water are collected into storage tank, and solid slag draws off dress woven bag storage.

- 80 mesh mixed powders after step A ball milling carry out various concentration powder under the conditions of 1.2L Hartmann Bomb and atmospheric air As a result the fire trial of cloud of dust cloud and different-energy can not all ignite, it is even more impossible to ignite, thus inspection result is its blast characteristics Belong to 0 grade (not exploding), it is safer.

The obtained roasting of detecting step A generates material no longer containing the fluoride other than metallic aluminum, aluminium nitride and calcirm-fluoride.

In step B reaction, it is 733kg that roasting, which generates material inventory,；The solid slag weight in wet base 360kg that step C is drawn off, after surveying moisture Give money as a gift weight 270kg；It calculates roasting and generates Al in material₂O₃Dissolution rate 77.5%.

Embodiment 2

Basic the step of repeating embodiment 1, prepares the water purification agent containing polyaluminium sulfate, and powder is described after difference is step A mill 700 DEG C of tunnel oven roastings are made roasting and generate material；Step B adds tap water 1200L, remaining tap water replaces with 1 step C of embodiment The washing water 1500L of filter residue water washing collection.

In step B reaction, added sulfuric acid concentration and quantity, roasting generate material inventory, slurry temperature control range, reaction Time is all identical, slurries filtrate pH3.9, Al₂O₃6.8m%, basicity 54；It calculates roasting and generates Al in material₂O₃Dissolution rate 80%, Reduce brought into the Al of washing water 1500L of 1 step C filter residue water washing collection of embodiment added by step B₂O₃Amount.

Embodiment 3

Basic the step of repeating embodiment 1, prepares the water purification agent containing polyaluminium sulfate, and difference is step A sodium hydroxide 550kg It is changed to sodium carbonate 650kg, calcium oxide 65kg is changed to the heavy calcium carbonate 120kg of 2.3 μm of equal partial size, and powder is in the tunnel after mill Kiln 850 DEG C of roasting 4hr in road are made roasting and generate material；Step B adds tap water 1200L, remaining tap water replaces with 2 step of embodiment The washing water 1500L of C filter residue water washing collection.

In step B reaction, added sulfuric acid concentration and quantity, roasting generate material inventory, slurry temperature control range, reaction Time is all identical, slurries filtrate pH3.9, Al₂O₃6.4m%, basicity 52；It calculates roasting and generates Al in material₂O₃Dissolution rate 76.4%, Brought into the Al of washing water 1500L of 2 step C filter residue water washing collection of embodiment added by step B is reduced₂O₃Amount.

Embodiment 4

Basic the step of repeating embodiment 1, prepares the water purification agent containing polyaluminium sulfate, and difference is that step B adds tap water 1200L, Remaining tap water replaces with the washing water 1500L of 3 step C filter residue water washing collection of embodiment, and the amount of added sulfuric acid is identical, roasting life At material inventory 870kg, slurry temperature control range is identical, reaction time 2.3hr, slurries filtrate pH4.0, Al₂O₃8.1m%, salt Base degree 70；It calculates roasting and generates Al in material₂O₃Dissolution rate 74% has reduced the supplemented 3 step C filter residue water of embodiment of step B slurries Wash brought into the Al of washing water 1500L of collection₂O₃Amount.Step C filter residue is washed with tap water 1500L, final outflow water pH6.

Embodiment 5

Basic the step of repeating embodiment 1, prepares the water purification agent containing polyaluminium sulfate, and difference is that step B first adds tap water 550L With the washing water 1500L of 4 step C filter residue water washing collection of embodiment, the amount of added sulfuric acid, roasting generate material inventory, slurries temperature Degree control range, reaction time are all identical, as a result slurries filtrate pH3.7, Al₂O₃9.0m%, basicity 50；It calculates roasting and generates material Middle Al₂O₃Dissolution rate 79.8%.Step C filter residue is washed with tap water 1500L, final outflow water pH6.

Embodiment 6

Basic the step of repeating embodiment 1, prepares the water purification agent containing polyaluminium sulfate, and step A difference is middle sodium hydroxide concentration 450kg；Step B difference is plus tap water 1200L, remaining tap water replace with washing for 5 step C filter residue water washing collection of embodiment Water 1500L is washed, roasting generates material inventory 905kg, and slurry temperature control range is identical, reaction time 2.5hr, slurries filtrate PH3.7, Al₂O₃6.8m%, basicity 48；It calculates roasting and generates Al in material₂O₃Dissolution rate 64%.Filter residue is washed with tap water 1800L It washs, final outflow water pH6.

Embodiment 7

Basic the step of repeating embodiment 1, prepares the water purification agent containing polyaluminium sulfate, and step A difference is middle Calcium Oxide Dosage 40kg；Step B difference is plus tap water 900L, remaining tap water replace with the washing of 6 step C filter residue water washing collection of embodiment Water 1800L, is added 40 m% hydrofluoric acid 30kg again after adding sulfuric acid to mix, roasting generates material inventory 730kg, slurry temperature control Range is identical, reaction time 2.3hr, slurries filtrate pH3.9, Al₂O₃6.9m%, basicity 52；It calculates roasting and generates Al in material₂O₃ Dissolution rate 76%.Filter residue is washed with tap water 1500L, final outflow water pH6.

In step B, added 40 m% hydrofluoric acid 30kg is the fluorine-containing Waste Sulfuric Acid to simulate the 1.37m% of concentration containing HF.

Embodiment 8

The composite water purifying agent containing polymeric aluminum sulfate iron is prepared as follows:

A. aluminium ash M1000kg and sodium hydroxide 550kg, calcium oxide 65kg is taken to put into ball mill, mixing and ball milling 5hr to -80 mesh, mill Powder 500 DEG C of roasting 3hr of tunnel oven air atmosphere described in embodiment 1 afterwards are made roasting and generate material；

B. in 5000L reaction tank, add tap water 1200L, add the washing water 1500L of 7 step C filter residue water washing collection of embodiment, Stirring is opened, adds 98m% industrial sulphuric acid 875kg, adds FeSO₄7H₂The ilmenite of O content 90m%-sulfuric acid method titanium pigment process units Ferrous sulfate by-product 600kg；Investment roasting generates material and reacts, 65-70 DEG C of slurries temperature control, suitably reduces roasting before overtemperature and generates material Feed temperature and charging rate, slurries pH be set to the aeration tube of reaction tank slurries bottom after being increased to 2.0 and (be uniformly arranged 40 sintered microporous gas distribution heads of powder of stainless steel) blast 20m³The oxygen of/hr leads to oxygen reaction time 3.1hr, until slurries are filtered Liquid pH3.5, investment roasting generates material 850kg altogether, surveys slurries filtrate Al₂O₃7.2m%, Fe₂O₃3.3m%, basicity 45；

C. step B slurries are filtered through leaf filter, and filtrate is the liquid water purification agent containing polymeric aluminum sulfate iron；Filter residue tap water 1500L washing, final outflow water pH6, washing water are collected into storage tank, and solid slag draws off dress woven bag storage.

Embodiment 9

B. in 5000L reaction tank, add tap water 800L, add the washing water 1500L of 8 step C filter residue water washing collection of embodiment, open Stirring, adds 98m% industrial sulphuric acid 875kg, 40 m% hydrofluoric acid 30kg, puts into aqueous red mud K820kg(butt 600kg), directly will 0.03MPa(gauge pressure) steam is passed through slurries and is allowed to be warming up to 80 DEG C, and maintains 80-85 DEG C of reaction 2hr of temperature；Roasting life is put into again It is reacted at material, 65-70 DEG C of temperature control, feed temperature and charging rate that roasting generates material, reaction time is suitably reduced before overtemperature 2.6hr, until slurries filtrate pH4.5, investment roasting generates material 850kg altogether, surveys Al₂O₃7.8m%, Fe₂O₃1.5m%, basicity 68；

C. step B slurries are filtered through leaf filter, are easily filtered, and filtrate is the liquid water purification agent containing polymeric aluminum sulfate iron；Filter residue is with originally Water 2000L washing, easy to wash, final outflow water pH6, washing water are collected into storage tank, and solid slag draws off dress woven bag storage.

In step B, added 40 m% hydrofluoric acid 30kg is the fluorine-containing Waste Sulfuric Acid to simulate 1.37 m% of concentration containing HF.

Embodiment 10

Basic the step of repeating embodiment 1, prepares the water purification agent containing polyaluminium sulfate, and difference is that the aluminium ash M of step A is changed to aluminium 1) grey N(-20 mesh, chemical component are shown in Table.

In step B reaction, added sulfuric acid concentration and quantity, roasting generate material inventory, slurry temperature control range, reaction Time is all identical, slurries filtrate pH3.7, Al₂O₃6.6m%, basicity 52；It calculates roasting and generates Al in material₂O₃Dissolution rate 79%.

Embodiment 11

A. aluminium ash M1000kg and sodium hydroxide 550kg, calcium oxide 65kg is taken to put into ball mill, mixing and ball milling 5hr to -80 mesh, mill Powder 600 DEG C of roasting 3hr of tunnel oven dehumidified air atmosphere described in embodiment 1 afterwards are made roasting and generate material；

B. in 5000L reaction tank, add tap water 800L, add the washing water 1500L of 8 step C filter residue water washing collection of embodiment, open Stirring, adds 98m% industrial sulphuric acid 875kg, 40 m% hydrofluoric acid 30kg, gradually puts into aqueous red mud K2050kg(butt 1500kg), Directly by 0.03MPa(gauge pressure) steam is passed through slurries and is allowed to be warming up to 80 DEG C, and maintains 80-85 DEG C of reaction 4hr of temperature；It puts into again Roasting generates material and reacts, 65-70 DEG C of slurries temperature control, and feed temperature and charging rate that roasting generates material are suitably reduced before overtemperature, Reaction time 2.3hr, until slurries filtrate pH4.0, investment roasting generates material 670kg altogether, surveys Al₂O₃8.7m%, Fe₂O₃3.4m%, salt Base degree 73；

Embodiment 12

By pH4.0 prepared by embodiment 11, Al₂O₃8.7m%, Fe₂O₃3.4m%, the filtrate containing polymeric aluminum sulfate iron of basicity 73 500L is spray-dried under the conditions of 175 DEG C of hot winds, and solid-state water purification agent product of the 230kg containing polyaluminium sulfate is made.

Embodiment 13

The basic operation for repeating 11 step A of embodiment, difference are that powder is at described 500 DEG C of tunnel oven dehumidified air atmosphere after grinding 3hr is roasted, roasting is made and generates material.

Embodiment 14

The basic operation for repeating 3 step A of embodiment, difference are described by aluminium ash M1000kg, sodium carbonate 650kg, calcium carbonate - 80 powder materials after powder 120kg ball milling, during 850 DEG C of roasting 4hr of the tunnel oven, tunnel oven uses dehumidified air atmosphere.

Embodiment 15

The basic operation for repeating 11 step B-C of embodiment, difference are added before step B puts into roasting generation material reaction 15kg calcium citrate, as the stabilizer of the prepared silicic acid containing polyaluminium sulfate, remaining process and the basic phase of result situation Together.

In each step A of above embodiments, the minitunnel kiln is that kiln, an endfeed are closed in the controllable electric heating of kiln atmosphere Closed feed space, discharge chamber are set up in other end discharging separately, and temperature is at 150 DEG C or more from feed space for feed end, material, the circulation of vital energy in the wrong direction Stream, feed end are the exhaust end of burner hearth gas, and discharge end is oxygen flow inlet end；Wherein tunnel in each step A of embodiment 1-10 Road kiln is into 25-26 DEG C, relative humidity 65-70%, that is, steam partial pressure 2.06-2.35kPa air, 11,13,14 step of embodiment Tunnel oven is into -45 DEG C of dew point of dehumidified air in A；Wherein the exhaust end air-flow of tunnel oven all omits in each step A of embodiment 1-9 There is ammonia odor, detection ammonia density is mostly 10-30 mg/m³, ammonia odor is just eliminated after absorption tower is handled；Embodiment 10 The exhaust end air-flow operator of tunnel oven can't smell ammonia odor in step A, detect ammonia density 3-5mg/m³；Embodiment 11,13, Tunnel oven end exhaust airstream does not have ammonia odor in 14 step A, and detection ammonia density is lower than 2mg/m³；The aluminium ash M, aluminium ash N raw material Using the preceding all last moisture absorption, aluminium ash in each embodiment step A, sodium hydroxide/sodium carbonate, calcic raw material ingredient, ball milling and After mill during the storage of powder, appropriate operation measure, the basic guarantee end moisture absorption are all taken, and stand after being packed into tunnel oven saggar 150 DEG C of closing feed spaces of tunnel oven are pushed into, and from the feed end fire box temperature after feed space all in 150 DEG C or more temperature Degree.

Above embodiments 1-11,15 step C in, during the filtering of leaf filter, residue washing, discovery is all that easy filter is easy It washes, the belt filter that high-efficient, employment is few, labor intensity is low, operates continuously can be used in production and complete.It is prepared to contain polymerised sulphur Sour aluminium or water purification agent solution containing polymeric aluminum sulfate iron survey F concentration and are all lower than 0.5mg/L, and ammonia nitrogen is lower than 100mg/L, and cyanogen is lower than Detection limit.The prepared water purification agent solution containing polyaluminium sulfate or containing polymeric aluminum sulfate iron, closed storage 3 months are all very stable, Purifying water effect is normal after storage, wherein the water purification agent solution containing polymeric aluminum sulfate iron prepared by embodiment 15, closed storage 6 months Very stable in the process, purifying water effect is normal after storage.Each filter residue of gained places 60 days in the process without any peculiar smell, more in air There is no ammonia odor；Add the stirring of 500ml distilled water to place 2 days 10g after gained each filter residue drying, takes and survey in supernatant F concentration all Lower than 0.5mg/L, lower than the prescribed limits 2.0mg/L of aluminum i ndustry pollutant emission standard GB 25465-2010, ammonia nitrogen is all lower than 0.1mg/L, cyanogen is lower than detection limit.

Comparative example 1

Basic the step of repeating embodiment 1, is operated, and is distinguished and is supplying sodium hydroxide in end in step A, using small in step B The inventory of type consersion unit and very little:

A. it takes aluminium ash M1000kg to put into ball mill, adds calcium oxide 65kg, ball milling 3hr to -80 mesh, powder 15kg is in institute after taking mill Tunnel oven and last dehumidified air 500 DEG C of roasting 3hr of atmosphere are stated, roasting material is made；

B. in 10L glassed steel reaction vessels, add water 3.7L, add 98m% sulfuric acid 1.2kg, stir, gradually put into roasting material 1.0kg, After controlling 85-90 DEG C of reaction 2hr of slurry temperature, slurries filtrate pH < 1；

C. step B slurries filter, and filter residue is washed to dry, quality 0.59kg after water outlet pH6.

Roasting material obtained by detecting step A, nitrogen aluminium 14.3m%；It is calculated according to test data total in step B roasting material Aluminium is converted into Al₂O₃Dissolution rate is lower than 30%；Step C filter residue has ammonia odor after placing in air 10 days, still have ammonia after placing 60 days Smell.Add the stirring of 500ml distilled water to place 2 days filter residue 10g, takes and survey F concentration 5.2mg/L in supernatant, exceed aluminum i ndustry 2.1 times of pollutant emission standard GB 25465-2010 prescribed limits 2.0mg/L.

Comparative example 2

Basic the step of repeating embodiment 1, is operated, and is distinguished and is supplying calcium oxide in end in step A, using small-sized in step B The inventory of consersion unit and very little:

A. aluminium ash M1000kg is taken to put into ball mill, adding sodium hydroxide 600kg ball milling 3hr to -80 mesh takes powder 15kg after mill to exist Roasting material is made in 500 DEG C of roasting 3hr of the tunnel oven and air atmosphere；

B. in 10L glassed steel reaction vessels, add water 3.7L, add 98m% sulfuric acid 1.2kg, stir, gradually put into 0.73kg roasting material, After controlling 85-90 DEG C of reaction 2hr of slurry temperature, slurries filtrate pH4.0；

C. step B slurries filter, and filter residue is washed to dry, quality 0.16kg after water outlet pH6；Survey 23 mg/L of fluorine content in filtrate.

Add the stirring of 500ml distilled water to place 2 days step C filter residue 10g, takes and survey F concentration 32mg/L in supernatant, exceed aluminium 15 times of emission of industrial pollutants standard GB 25465-2010 prescribed limits 2.0mg/L.

Comparative example 3

Basic step B, C for repeating comparative example 2 is operated, and difference, which is to put into step B, first adds -60 mesh lime before roasting material Mountain flour 60g:

B. in 10L glassed steel reaction vessels, add water 3.7L, add 98m% sulfuric acid 1.2kg, stir, add -60 mesh agstone 60g anti- 2 step A roasting material of 0.73kg comparative example gradually should be put into completely, after controlling 85-90 DEG C of reaction 2hr of slurry temperature, slurries filtrate pH4.2；

C. step B slurries filter, and filter residue is washed to dry, quality 0.14kg after water outlet pH6；Survey 0.64 mg/ of fluorine content in filtrate L。

Add the stirring of 500ml distilled water to place 2 days step C filter residue 10g, takes and survey F concentration 45mg/L in supernatant, exceed aluminium 21.5 times of emission of industrial pollutants standard GB 25465-2010 prescribed limits 2.0mg/L.

In the above various embodiments, comparative example, for the air of tunnel oven inlet end for inbound traffics, oxygenous amount is aluminium 3-5 times of amount of oxygen needed for grey calcined metal aluminium, nitridation reactive aluminum generate aluminium oxide.

The main composition of 1 aluminium of table ash, red mud, m%

。

In the present invention, aluminum solutions containing polyaluminum sulfate, Al in ferrous solution containing polyaluminium sulfate₂O₃Content, Fe₂O₃Content, alkali Degree is measured by water treatment agent aluminium polychloride GB/T 26824--2011 method；Micro ammonia content is tried by Na Shi in roasting exhaust The measurement of agent spectrophotometry；F concentration passes through alizarin sulfonic acid zirconium colorimetric method for determining in solution.Roasting generates whether material contains metallic aluminium It is qualitative: take 0.3-0.5g be added 2-5ml40%TiCl₄Solution then restores containing metallic aluminium and generates TiCl₃Aobvious purple；Whether contain The detection of aluminium nitride: taking 0.3-0.5g that 10-20ml 1+1 sulfuric acid or 1:1 phosphorus sulphur nitration mixture is added, cool down after heating molten sample, is added dropwise 20-40% caustic lye of soda has ammonia odor then nitrogen aluminium, and quantitative, ammonia still process, 2% borate absorb, 0.1mol/L sulfuric acid titrates can Survey nitridation aluminium content；It is placed with ammonia odor in long-time humid air and then illustrates nitrogen aluminium.Roasting generates material and carries out XRD test, Judged whether by test result and spectrogram containing the fluoride other than metallic aluminum, aluminium nitride and calcirm-fluoride.

Claims

1. a kind of method by aluminium ash, water purification agent of the sulfuric acid preparation containing polyaluminium sulfate, includes the following steps:

B. roasting is taken to generate material, the aqueous solution with sulfur acid, reaction prepares slurries, it reacts to slurries filtrate pH3.0-4.0, Al₂O₃5-12m%, basicity 40-75；

2. the method by aluminium ash, water purification agent of the sulfuric acid preparation containing polyaluminium sulfate according to claim 1, which is characterized in that When using sodium hydroxide in step A and the mass ratio of aluminium ash is (0.5-0.8): 1；And/or when using sodium carbonate and the matter of aluminium ash Amount is than being (0.5-1.0): 1；And/or the fluorine-containing calcirm-fluoride that is converted into of calcic raw material institute's calcic and aluminium ash institute deducts aluminium ash institute Calcium needed for calcic, amount ratio are (3-7): 1.

3. the method by aluminium ash, water purification agent of the sulfuric acid preparation containing polyaluminium sulfate according to claim 1, which is characterized in that 500-850 DEG C of maturing temperature in step A；And/or the oxidizing atmosphere is formed by air-supplied or oxygen-enriched air.

4. the method by aluminium ash, water purification agent of the sulfuric acid preparation containing polyaluminium sulfate according to claim 1, which is characterized in that Oxidizing atmosphere described in step A is formed by feeding the air or oxygen-enriched air that are dehydrated or dehumidify.

5. the method by aluminium ash, water purification agent of the sulfuric acid preparation containing polyaluminium sulfate according to claim 1, which is characterized in that Sulfuric acid used is fluorine-containing Waste Sulfuric Acid, iron content Waste Sulfuric Acid or Waste Sulfuric Acid containing aluminium in step B；And/or in step B in reaction process, lead to The temperature that control roasting generates the investment rate control reacting slurry of material is crossed, and/or roasts the input amount for generating material by control Control the basicity of slurries filtrate.

6. according to claim 1 by the method for aluminium ash, water purification agent of the sulfuric acid preparation containing polyaluminium sulfate, which is characterized in that Citric acid, calcium citrate or the sodium citrate of 0.1-0.5m% is added in step B in reaction process, as stabilizer.

7. the method by aluminium ash, water purification agent of the sulfuric acid preparation containing polyaluminium sulfate according to claim 1, which is characterized in that Step C filter residue fresh water wash, cleaning solution go step B prepared as diluting concentrated sulfuric acid sulfur acid aqueous solution water source.

8. the method by aluminium ash, water purification agent of the sulfuric acid preparation containing polyaluminium sulfate according to claim 1, which is characterized in that Ferric sulfate or its solution or sulfuric acid sulfur acid iron used are added in step B slurries, or is added by Bayer process red mud or Iron Ore Powder, Or sulfuric acid used first reacts with Bayer process red mud or Iron Ore Powder and generates the desired amount of ferric sulfate, prepares answering containing polymeric aluminum sulfate iron Close water purification agent；And/or Fe in step B slurries filtrate₂O₃1-3.5m%。

9. according to claim 1 by the method for aluminium ash, water purification agent of the sulfuric acid preparation containing polyaluminium sulfate, which is characterized in that Ferrous sulfate or its solution are added in step B slurries or sulfuric acid sulfur acid used is ferrous, or is added by waste iron filing and sulfuric acid reaction The solution or sulfuric acid used of the sulfur acid ferrous iron of generation first add waste iron filing reaction to generate the desired amount of ferrous sulfate, and described It prepares and blasts air, oxygen-enriched air, oxygen in the reaction process of slurries during pH2-4.0, or hydrogen peroxide solution, secondary chlorine is added Acid sodium solution, calcium hypochlorite solution are handled ferrous oxidising as ferric iron, compound water purification of the generation containing polymeric aluminum sulfate iron Agent.

10. the method by aluminium ash, water purification agent of the sulfuric acid preparation containing polyaluminium sulfate, feature exist according to claim 1 In the raw material or ingredient that step C solid slag is used as sintering building materials, is sintered cement.