CN102249326A - Method for preparing chromium hydroxide by chromium slag with combined production of calcium magnesium aluminium mixed chloride - Google Patents
Method for preparing chromium hydroxide by chromium slag with combined production of calcium magnesium aluminium mixed chloride Download PDFInfo
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- CN102249326A CN102249326A CN2010105981636A CN201010598163A CN102249326A CN 102249326 A CN102249326 A CN 102249326A CN 2010105981636 A CN2010105981636 A CN 2010105981636A CN 201010598163 A CN201010598163 A CN 201010598163A CN 102249326 A CN102249326 A CN 102249326A
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Abstract
The invention belongs to the technical field of three-waste treatment and comprehensive utilization in chromium compound manufacturing enterprises, and particularly relates to a method for preparing chromium hydroxide by chromium slag with combined production of calcium magnesium aluminium mixed chlorides; the invention mainly comprises the following steps: performing acidolysis of chromium slag by hydrochloric acid, filtering, depositing the filtrate, separating the depositing solution, performing deep processing of the filtrate and the filter cake to obtain chromium hydroxide and calcium magnesium aluminium mixed chlorides; The invention can not only swallow up waste slag completely so as to reduce environmental pollution of the waste slag, but also can obtain valuable chromium hydroxide and calcium magnesium aluminium mixed chlorides; the invention not only has significant social benefits and economic benefits, but also has simple process and production equipment, and is a practical method for treatment and utilization.
Description
Technical field
The present invention relates to the technical field of the disposal of three wastes of chromium cpd manufacturing concern and utilization, especially a kind of method for preparing chromium hydroxide coproduction calcium, magnesium, aluminium mixed chloride with the chromium slag.
Technical background
The solid waste of chromium salt production is meant mainly that in the sodium dichromate 99 production process chromite is generally called the chromium slag through the residue with the water extraction sodium dichromate 99 after the roasting.The chromium slag is to belong to severe toxicity, dangerous waste residue, and its outward appearance has Huang, color such as black, reddish brown.Often contain oxide compounds such as calcium, magnesium, iron, aluminium and chromium sesquioxide, water-soluble chromic acid sodium, solubility in acid Sodium chromate etc. in the chromium slag.The main sexavalent chrome of the toxicity of chromium, chromic toxicity mainly come from its strong oxidizing property to be caused organic corrosion and destruction, also is the carcinogenic substance of MA.
Because raw materials used, production technique and prescription are different, the turnout of chromium slag is different thereupon with composition.After testing, consisting of of chromium slag: chromium sesquioxide accounts for 2.5%～4% of total slag amount percentage ratio, water-soluble sexavalent chrome accounts for 0.28%～1.34% of total slag amount percentage ratio, the solubility in acid sexavalent chrome accounts for 0.9%～1.4% of total slag amount percentage ratio, calcium oxide accounts for 29%～36% of total slag amount percentage ratio, magnesium oxide accounts for 20%～33% of total slag amount percentage ratio, and aluminium sesquioxide accounts for 5%～8% of total slag amount percentage ratio, 8%～11% of the total slag amount of silica comprises percentage ratio.
Because the toxicity of chromium slag is very big, in a single day soil and underground water are subjected to chromic pollution, and soil can not farming, and underground water can't be quoted, if can not take special control measures, this pollution can't be eliminated decades, and can't recover ecological decades on every side.Hence one can see that, chromium slag such as the untimely processing of detoxifying, in case polluted environment, particularly underground water and soil, its consequence is very serious.
When no reductive agent, the aqueous solution of sodium dichromate 99 contains the hexavalent chromium of severe toxicity, the air storage of chromium slag, drenched by sleet soaks, contained sexavalent chrome is dissolved the water or enter in river, the lake of permeating the ground, contaminate environment, in the severe contamination band in the water content of 6-valence Cr ions can be up to every liter tens of milligrams, surpass the drinking water standard several times.Sexavalent chrome, chromium cpd and chromium cpd aerosol etc. simultaneously also can endanger human and livestock health in a variety of forms, so the storing up the field and must take anti-the blending of floor file to add the canopy cover of chromium slag.
In order to prevent the harm of chromium slag, common way is that it is carried out pyroprocessing, eliminates its toxicity.Having under the acidic conditions of reductive agent in addition, or under the alkaline condition that alkali metalsulphide, sulfohydrate are arranged, or under the high temperature that has sulphur, carbon and carbide to exist, anoxia condition, sexavalent chrome is all reducible to be the less trivalent chromium of toxicity.At present, the utilization of chromium slag mainly contains the following aspects:
1. produced sintering brick: with chromium slag drying, pulverizing, press the mixed batching of chromium ground-slag 40% and clay 60%, make adobe, kiln-firing.In high temperature and strong reducing property environment, hexavalent chrome reduction is water-fast chromium sesquioxide, eliminates severe toxicity, and prepared brick material can reach building requirements.
2. make high-strength chromium barium brick: with 5 parts of chromium slags and 3 parts of barium carbonate slag mixing and water addings 40%, wet-milling in ball mill.Sexavalent chrome in the chromium slag becomes water-fast baryta yellow, and a part changes into trivalent chromium; By 3 parts of chromium barium slag slurries and 2 parts of cinder batchings,, make adobe through rolling and boiling in a covered pot over a slow fire material; Through intensification, constant temperature, cooling respectively 2 hours, under 8 barometric points, carry out autoclave curing then, make chromium barium brick.Contain more magnesium oxide in the chromium slag, volume can expand, and need deposit for some time, uses after the volume stability.
3. make the cast stone of chromium slag: with 30% chromium slag, 25% silicate and 45% cinder batching, mix 3～5% ferric oxide again, through fusion-cast, recrystallization annealing temperature, make ultimate compression strength and be 4800～5500 kilogram forces/centimetre high strength, wear-resistant, etch-proof cast stone.
4. make cement: press ordinary Portland cement with raw materials such as chromium slag, Wingdale, clays and prepare burden, can calcining cement clinker, be used for making cement; Utilize chromium slag after the carbon reduction with granulated blast-furnace slag, bessemer furnace slag and Portland clinker, add 5% left and right sides gypsum, also can make few grog iron and steel slag cement.
In addition, the chromium slag also can replace chromite ore fine, as the emerald green tinting material of glass; Shrend chromium slag also can be used as cement additive, mineral wool raw materials, heat-resistant adhesive gel material, fused cement raw material etc.In the chromium slag of Japan after removing poison, add reductive agents such as ferrous sulfate, iron protoxide, make the plasticity-solidification material or make the gypsum sheet material stopping composition.
Though the chromium slag can both be to a certain degree disposed in above-mentioned these utilizations, because the chromium slag has toxicity, be difficult to transportation, its utilization does not open up new prospect as yet; When the chromium slag is handled, be confined to eliminate its toxicity and do not make full use of element that it contained, valuable; Chromium slag also of no use prepares the relevant report of the method for chromium hydroxide coproduction calcium, magnesium, aluminium mixed chloride at present.
Summary of the invention
The invention provides and a kind ofly prepare the method for chromium hydroxide coproduction calcium, magnesium, aluminium mixed chloride with the chromium slag, this method not only technology is simple, and can also make multiple value product when can effectively handle waste residue.
To achieve the above object, technical scheme of the present invention is:
A kind ofly prepare the method for chromium hydroxide coproduction calcium, magnesium, aluminium mixed chloride, comprise being prepared as follows step with the chromium slag:
Steps A, the chromium slag packed into fully stir in first corrosion-resistant reactor that fills hydrochloric acid, wherein said chromium slag carries out acidolysis reaction with the trivalent chromium converted and sexavalent chrome and hydrochloric acid according to pure mass ratio respectively at 1: 0.47, and reaction obtains the mixture I of chromium chloride and calcium, magnesium, aluminium mixed chloride;
Step B, gained mixture I in the steps A is filtered with first strainer;
Step C, send to deep processing separately with filtering the gained filter cake among the step B;
Step D, be sent to slurry tank, toward slurry tank in, add entry again, make the mixtures II of chromium chloride hydrolysis formation calcium, magnesium, aluminium mixed chloride and chromium hydroxide precipitation filtering gained filtrate among the step B;
Step e, gained mixtures II among the step D is filtered with second strainer;
Step F, with gained filter cake in the step e successively with first water cooler, first washing and spin-drying machine, first moisture eliminator, first pulverizer cool off, wash drying, dry and pulverize after check the weight and be packaged to be the chromium hydroxide product;
Step G, be calcium, magnesium, aluminium mixed chloride 10 with gained filtrate in the step e.
Preferably, employed hydrochloric acid is that concentration of volume percent is 60%～75% hydrochloric acid soln among the described step C.
Reaction principle of the present invention is:
Chromic reaction: Cr
2O
3+ 6HCl=====2CrCl
3+ 3H
2O
CrCl
3+3H
2O＝＝＝＝＝Cr(OH)
3+3HCl
Chromic reaction: 2CrO
3+ 12HCl=====2CrCl
3+ 3Cl
2+ 6H
2O
CrCl
3+3H
2O＝＝＝＝＝Cr(OH)
3+3HCl
The reaction of calcium, magnesium, aluminium:
CaO+2HCl＝＝＝＝＝CaCl
2+H
2O
MgO+2HCl＝＝＝＝＝MgCl
2+H
2O
Al
2O
3+3HCl＝＝＝＝＝AlCl
3+3H
2O
The present invention carries out the acidolysis after-filtration with the chromium hydrochloric acid for dreg earlier, filtrate is carried out sedimentation again, behind the separate and subside liquid, filter cake obtains the chromium hydroxide product after washing drying, drying and crushing, and filtrate is that calcium, magnesium, aluminium mixed chloride and filtrate make the Manganous chloride tetrahydrate product at last through underpressure distillation; The present invention can as clean as a pennyly gulp down waste residue, alleviates the pollution of waste residue to environment; Can make valuable chromium hydroxide and calcium, magnesium, aluminium mixed chloride again, not only have remarkable social benefit and economic benefit, and technology and production unit are simple, be a kind of relatively actual processing and utilize method.
Description of drawings
Fig. 1 is the process flow sheet for preparing the method for chromium hydroxide coproduction calcium, magnesium, aluminium mixed chloride with the chromium slag;
Wherein:
1-first corrosion-resistant reactor, 2-first strainer, 3-slurry tank, 4-second strainer, 5-first water cooler, 6-first washing and spin-drying machine, 7-first moisture eliminator, 8-first pulverizer, 9-chromium hydroxide product, 10-calcium, magnesium, aluminium mixed chloride.
Concrete embodiment
A kind ofly prepare the method for chromium hydroxide coproduction calcium, magnesium, aluminium mixed chloride, comprise being prepared as follows step with the chromium slag:
Steps A, (wherein with chromium slag 1000Kg, trivalent chromium is 30Kg, sexavalent chrome is 10Kg, calcium oxide is 300Kg, magnesium oxide is 250Kg, aluminum oxide is 60Kg) 1 li of first corrosion-resistant reactor that fills hydrochloric acid of packing into fully stirs, and wherein said chromium slag 1: 0.47 carries out acidolysis reaction with hydrochloric acid according to pure mass ratio with trivalent chromium and the sexavalent chrome of converting respectively, reacts the mixture I that obtains chromium chloride and calcium, magnesium, aluminium mixed chloride; Hydrochloric acid is that concentration of volume percent is 72% hydrochloric acid soln; Wherein, the hydrochloric acid concentration of volume percent can be obtained than good yield between 60%～75%.
Step B, gained mixture I in the steps A is filtered with first strainer 2;
Step C, send to deep processing separately with filtering the gained filter cake among the step B;
Step D, be sent to slurry tank 3, toward slurry tank 3 in, add entry again, make the mixtures II of chromium chloride hydrolysis formation calcium, magnesium, aluminium mixed chloride and chromium hydroxide precipitation filtering gained filtrate among the step B;
Step e, gained mixtures II among the step D is filtered with second strainer 4;
Step F, with gained filter cake in the step e successively with first water cooler 5, first washing and spin-drying machine 6, first moisture eliminator 7, first pulverizer 8 cool off, wash drying, dry and pulverize after check the weight and be packaged to be 15.49Kg chromium hydroxide product 9, (that wherein trivalent chromium produced is 13.24Kg, and that sexavalent chrome produced is 2.21Kg);
Step G, be 402.49Kg calcium, magnesium, aluminium mixed chloride product 10 with gained filtrate in the step e, (wherein, calcium hydroxide is 214.65Kg, and magnesium hydroxide is 153.46Kg, and aluminium hydroxide is 34.38Kg);
The foregoing description is preferred embodiment of the present invention, is not to be used for limiting the scope of the present invention, so all equivalences of being done with described feature of claim of the present invention and principle change or modify, all should be included within the claim scope of the present invention.
Claims (2)
1. prepare the method for chromium hydroxide coproduction calcium, magnesium, aluminium mixed chloride with the chromium slag, it is characterized in that, comprise being prepared as follows step:
Steps A, chromium slag first corrosion-resistant reactor (1) lining that fills hydrochloric acid of packing into is fully stirred, wherein said chromium slag carries out acidolysis reaction with the trivalent chromium converted and sexavalent chrome and hydrochloric acid according to pure mass ratio respectively at 1: 0.47, and reaction obtains the mixture I of chromium chloride and calcium, magnesium, aluminium mixed chloride;
Step B, gained mixture I in the steps A is filtered with first strainer (2);
Step C, send to deep processing separately with filtering the gained filter cake among the step B;
Step D, be sent to slurry tank (3), toward slurry tank (3) in, add entry again, make the mixtures II of chromium chloride hydrolysis formation calcium, magnesium, aluminium mixed chloride and chromium hydroxide precipitation filtering gained filtrate among the step B;
Step e, gained mixtures II among the step D is filtered with second strainer (4);
Step F, with gained filter cake in the step e use successively first water cooler (5), first washing and spin-drying machine (6), first moisture eliminator (7), first pulverizer (8) cool off, wash drying, dry and pulverize after check the weight and be packaged to be chromium hydroxide product (9);
Step G, be calcium, magnesium, aluminium mixed chloride (10) with gained filtrate in the step e.
2. prepare the method for chromium hydroxide coproduction calcium, magnesium, aluminium mixed chloride according to claim 1 is described with the chromium slag, it is characterized in that employed hydrochloric acid is that concentration of volume percent is 60%～75% hydrochloric acid soln among the described step C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105981636A CN102249326A (en) | 2010-12-21 | 2010-12-21 | Method for preparing chromium hydroxide by chromium slag with combined production of calcium magnesium aluminium mixed chloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105981636A CN102249326A (en) | 2010-12-21 | 2010-12-21 | Method for preparing chromium hydroxide by chromium slag with combined production of calcium magnesium aluminium mixed chloride |
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|---|---|
| CN102249326A true CN102249326A (en) | 2011-11-23 |
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| CN2010105981636A Pending CN102249326A (en) | 2010-12-21 | 2010-12-21 | Method for preparing chromium hydroxide by chromium slag with combined production of calcium magnesium aluminium mixed chloride |
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2010
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Address after: 523000, room five, building 508, Jinhai building, Dongcheng District Tong Road, Dongguan, Guangdong Applicant after: Wang Jiaxing Address before: Wushi Village Primary School in Dongguan city of Dongcheng District province Guangdong road 523000 Lane 1 No. 6 main mountain Applicant before: Wang Jiaxing |
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Application publication date: 20111123 |