CN104762637A - Comprehensive utilization method and device for acid dissolution extraction of valuable element chromium silicon iron magnesium aluminum nickel from chromite - Google Patents

Comprehensive utilization method and device for acid dissolution extraction of valuable element chromium silicon iron magnesium aluminum nickel from chromite Download PDF

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CN104762637A
CN104762637A CN201510077631.8A CN201510077631A CN104762637A CN 104762637 A CN104762637 A CN 104762637A CN 201510077631 A CN201510077631 A CN 201510077631A CN 104762637 A CN104762637 A CN 104762637A
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liquid
chromite
solid
acid
ion
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CN104762637B (en
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于志远
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于志远
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Abstract

The invention discloses a comprehensive utilization method for acid dissolution extraction of valuable element chromium silicon iron magnesium aluminum nickel from chromite, first the chromite is crushed and ground into micro powder, the micro powder is blew with air for oxidation at the bottom of an electrode oxidation pool for oxidation of ferrous ion into iron ion; chrome spinel lattice is destructed, the oxidized chromite micro powder is reacted with sulfuric acid in a high temperature high pressure reaction kettle to produce a mixed liquid containing chromium sulfate, magnesium sulfate, aluminum sulfate, ferric sulfate and nickel sulfate and a deposit mainly comprising silicon dioxide and insoluble minerals under the oxidation-catalyst effect; after solid-liquid separation, a solid is again purified to obtain white carbon black; and chromium sulfate hexahydrate, high purity magnesium hydroxide, high purity aluminum hydroxide, high purity ferrous oxalate and nickel sulfide can be obtained by liquid fractional extraction of liquid phase. All the valuable elements, acids, alkalis, water and other raw materials can be extracted for cyclic utilization after front oxidation and high temperature and high pressure acid dissolution of the chromite ore powder.

Description

The method of comprehensive utilization of chromite acid-soluble extraction valuable element ferrochrome silicon magnalium nickel and device thereof
Technical field
The comprehensive mining that the present invention relates to chromite utilizes, and belongs to domain of inorganic chemistry.
Background technology
Chromite is a kind of mineral, and main component is the oxide compound of iron, aluminium, magnesium and chromium: (Fe, Mg) Cr2O4, is the one of spinel.It is unique minable chrome ore, and mineralogical composition is more complicated, and the content of magnesium is indefinite, sometimes also containing aluminium and ferro element.Nature containing chrome mineral about 30 kinds, but there is industrial value only have chromite, China common are chromite, alumcromite and rich picotite.
Chromite is commercially generally divided into 3 classes by service requirements
(1) high chromium chromite (metallurgy is used), containing more than Cr2O348%, Cr2O3/FeO ratio is large.Chromite is mainly used to produce ferrochrome and chromium metal
(2) high ferro chromite (chemical industry is used), containing more than Cr2O350%, few containing SiO2, Al2O3.Be mainly used to produce sodium dichromate 99, and then produce other chromium cpds, for industry such as pigment, weaving, plating, process hides, also can make catalyzer and activator etc.
(3) high alumcromite (used for refractory material), containing Cr2O330% ~ 35%, many containing Al2O3, MgO.Chromite is used for manufacturing chrome brick, magnesite chrome brick and other special refractories.
Be more than the main aspect that utilizes of chromite, processing method, with pyrogenic process and electric furnace, utilizes higher-grade chromite.Utilizing of low-grade chromite is low.
The existing basic circuit producing chromium cpd from chromite has three kinds.
The first is alkaline oxygenated route, and namely chromite reacts in air or pure oxygen with alkali, and trivalent chromium oxidation is sexavalent chrome, extracting sulfuric acid chromium.
The second is high temperature reduction route, and namely chromite makes carbon ferrochrome with reductive coke in electric furnace.
The third circuit is referred to as acid pasting, and namely the direct same sulfuric acid reaction of chromite, produces the compound of chromium after obtaining chromium sulfate solution.CNOOC Tianjin chemical design institute Mr. Ji Zhu has done detailed elaboration in inorganic chemicals industry magazine the 44th volume the 12nd phase in December, 2012 to the acid-soluble technology both domestic and external of chromite.
Chromite results from ultrabasic rocks, and serpentinite is ultrabasic rocks alteration, and both interosculate and have different place.Chromite enrichment in ultrabasic rocks generates picotite, just has the whole elements in serpentinite in picotite.The crystalline network of chromite is more insoluble in acid than serpentinite.
Technology and the technique of serpentinite acid-soluble extraction valuable element are ripe, and chromite acid-soluble be not very perfect, existing invention and method not high to the chromite utilization ratio lower than less than 30%, utilize and also do not reach rational economic benefit.
The solid insoluble produced in chemical reaction, in order to remove the ionic impurity that its surface is carried, at present, the method only adopting conventional water to rinse in this area, if just rest on laboratory stage, embodies the consumption of not water outlet, once have high input in scale production, the consumption of water is very huge.Especially in water-deficient areas such as Xinjiang, the method for this removal of impurities plain more outstanding.Further, this method removal of impurities, can not be thoroughly clean by the ion remaval on solid sediment surface completely, do not reach real high-purity object.
Summary of the invention
The technical problem to be solved in the present invention overcomes existing defect, provide a kind of method making full use of low-grade chromite, the method for comprehensive utilization of little, the efficient reusable edible chromite of this method three waste discharge acid-soluble extraction valuable element ferrochrome silicon magnalium nickel;
It is ionic membrane knot screen used in aforesaid method that another order of the present invention has;
Another object of the present invention utilizes said apparatus to the impurity removal process of the soluble ion of solid product surface attachment in chemical reaction.
Object of the present invention carrys out specific implementation by the following technical programs:
A kind of ionic membrane knot screen, comprises anolyte compartment, cathode compartment, supplies room, supplies room between anolyte compartment and cathode compartment,
Wherein,
Be provided with anode in described anolyte compartment, and separated by anionic membrane between supplies room;
Be provided with negative electrode in described cathode compartment, and separated by cationic membrane between supplies room;
Be provided with the material that solid insoluble is housed in described supplies room blue, bottom is provided with whipping appts.
Further, described anolyte compartment is also provided with the first pure water inlet, the first discard solution discharge port, the first waste gas collection device; Described cathode compartment is also provided with the second pure water inlet, the second discard solution discharge port, Hydrogen collection device; Described supplies room is also provided with the 3rd pure water inlet, the 3rd discard solution discharge port, material main-inlet, discharge of materials mouth.
Further, described zwitterion film is equipped with ionic membrane protection web plate;
Preferably, described material is blue is porous filter indigo plant;
Preferred further, described whipping appts adopts ultrasonic vibration agitator.
An impurity removal process for chemical precipitates intermediate ion impurity, utilizes above-mentioned device, comprises the steps:
1) before electrolysis: the material indigo plant solid product produced in chemosynthesis being placed in supplies room, inject enough pure water in anode room, cathode compartment and supplies room, under agitation make the soluble ion being attached to solid product surface fully be dissolved in pure water;
2) electrolysis: under the effect of electrode, negatively charged ion is gas by anionic membrane at anode electrolysis, gas recovery, and positively charged ion is metal and basic metal or precipitation at negative electrode by electrolysis by cationic membrane, when negative electrode has hydrogen to produce, stops electrolysis;
3) after electrolysis: the liquid of first draining in two electrode vessels, and then the water in supplies room of draining, the soluble ion Impurity removal of chemical precipitates is complete.
A method of comprehensive utilization for chromite acid-soluble extraction valuable element ferrochrome silicon magnalium nickel, be first micro mist by chrome ore crushing grinding, micro mist blows atmospheric oxidation in anodizing pond, makes ferrous ions be iron ion, destroys picotite lattice; Chromite micro mist after oxidation in the reactor of high temperature, high pressure with sulfuric acid reaction, under the effect of oxidation-catalyzer, generating the mixing liquid of sulfur acid chromium, magnesium sulfate, Tai-Ace S 150, ferric sulfate and single nickel salt and silicon-dioxide and insoluble mineral is main throw out; By solid-liquid separation, solids is through obtained white carbon black of again purifying; The fractional extraction of liquid phase liquid goes out six water chromium sulphates, high purity magnesium hydroxide, high purity aluminium hydroxide, high-purity oxalic acid ferrous iron, nickelous sulfide.
Preferably, the method for comprehensive utilization of above-mentioned chromite acid-soluble extraction valuable element ferrochrome silicon magnalium nickel, concrete technology step is as follows:
1) chromite ore processing
Be processed into through broken, ball milling the powder that granularity is less than 100 microns after chromite ore exploitation, be placed in anodizing groove, breeze adds water, and anodizing trench bottom is blown into air; Anodizing groove works, and makes breeze Quick Oxidation.Breeze picotite lattice after oxidation is destroyed, and is easier to follow-up acid dissolution.
2) acid-soluble
Breeze is placed in high-temperature high-pressure reaction kettle and reacts with sulphuric acid soln, adds catalysis-oxygenant in reaction, and the reaction times is 1 little of 12 hours;
3) solid-liquid separation
Use whizzer or film, molecular sieve filtration, solid-liquid is thoroughly separated;
4) the producing of white carbon black
After separation with silicon-dioxide be main component solid again ball milling slurrying react with strong acid in high-temperature high-pressure reaction kettle, the impurity in silicon-dioxide is fully reacted, by solid-liquid separation, liquid enter waste water operation carry out process Posterior circle utilize.Silica solid cleans through pure water, enters the electron ion film knot screen removal of impurities described in any one of claim 1 to 3; Silicon-dioxide after removal of impurities and sodium hydroxide solution react, with hydrothermal method high purity superfine white carbon black.The white carbon black produced enters the removal of impurities of electron ion film device again, and removal of impurities post-drying is packed.
5) heavyly ironly Ferrox is got
Liquid liquid after filtration adds hydrogen peroxide in settling bath makes a small amount of ferrous ion complete oxidation in liquid be iron ion, makes the ferrous sulfate complete oxidation in liquid be ferric sulfate; After testing without after ferrous ion in solution, detect the concentration of iron ion in solution, calculate after adding the amount of oxalic acid, add oxalic acid, oxalic ferrous precipitation, carry out solid-liquid separation, liquid enters next step link;
By isolated solid-state Ferrox after pure water cleaning, mix with pure water in above-mentioned electron ion film knot screen and carry out removal of impurities, obtain the oven dry of high-purity oxalic acid ferrous iron and pack;
6) six hydrated sulfuric acid chromium are extracted
Liquid after being separated in step 5), the temperature of 15 ± 2 DEG C, adds salting-out agent vibration slaking 24 hours, six hydrated sulfuric acid chromium crystallizations, solid-liquid centrifugation is separated, and solid drying packaging is preserved, liquid fractionation by distillation ethanol, ethanol reclaims and continues to utilize, and the liquid after separating alcohol enters next step link;
7) extraction of magnesium hydroxide and aluminium hydroxide
Add excessive sodium hydrate or ammonia soln in the liquid be separated in step 6), produce the mixing solutions of magnesium hydrate precipitate and sodium sulfate, sodium metaaluminate and Sodium chromate, filter and obtain magnesium hydroxide solid; After the cleaning of magnesium hydroxide solid pure water, in above-mentioned electron ion film knot screen after removal of impurities, obtain high purity magnesium hydroxide, drying is packed.
Add excess carbon dioxide gas in filtered fluid, obtain aluminum hydroxide precipitation, through solid-liquid separation, solid aluminum hydroxide is with after pure water cleaning, removal of impurities in above-mentioned electron ion film knot screen, more further with pure water cleaning, reach the requirement post-drying packaging of high purity product;
8) heavy nickel
Add sodium sulphite precipitated the sodium sulphite add-on that the content meter that adds nickel ion after testing in the solution after magnesium hydroxide and aluminium hydroxide calculates in step 7) after and generate nickel sulphide precipitation, after filtration, obtain nickelous sulfide;
9) filtrate process
The liquid obtained after step 8) is mainly sodium sulfate liquid, after crystallization, obtain sodium sulfate crystal
Preferably, in described step 1), add water and make breeze water tariff collection at 10wt%-15wt%.
Preferably, described step 2) in, temperature of reaction kettle is 120 DEG C ~ 200 DEG C, pressure is 200-300 rev/min in 0.5MPa ~ 1MPa, stirring velocity;
Preferred further, temperature of reaction kettle is 150 DEG C, pressure is 300 rev/min in 0.8MPa, stirring velocity.
Preferably, described step 2) in, the concentration of sulfuric acid is 50wt%-70wt%, and the mass ratio of breeze and sulfuric acid is 1:2 to 1:3;
Preferred further, the concentration of sulfuric acid is 60wt%, and the mass ratio of breeze and sulfuric acid is 1:2.8;
Preferably, described step 2) in, described catalysis-oxygenant adopts hydrogen peroxide or perchloric acid, makes ferrous iron be oxidized to ferric iron completely.
Preferably, in described step 6), described salting-out agent are the ethanol of more than 99.5%, and the amount added is the 50wt%-80wt% of amount of liquid.
Beneficial effect of the present invention:
The present invention by be oxidized the breeze front end of chromite, acid-soluble, extract whole valuable elements, take full advantage of chromite, the feedstock circulation utilizations such as acid, alkali, water, only have minimum waste discharge, reach good economic benefit.
In prior art, traditional chromium iron ore is added the furnace charges such as coke and produces ferrochrome by electric furnace, energy consumption is high, pollution is large, can only utilize higher-grade chromite, utilizes element to only have chromium and iron.Chemical industry aspect, chromite and sodium hydroxide are calcined and are produced sodium dichromate 99 in rotary kiln, can only use higher-grade chromite, utilize element to only have chromium.This method energy consumption is high, pollution is large, waste residue is many.Another high alumina height chromium chromite is used for producing refractory brick, and the chromite rare to China is great waste.
The present invention uses High Temperature High Pressure acid pasting to fully utilize chromite, and ultralow grade all can be processed to higher-grade chromite, and ultralow grade chromite can utilize the utilization of the elements such as silicon, magnesium, aluminium, iron, nickel to reach good economic benefit.Material sulfuric acid used in the present invention, sodium hydroxide, ammoniacal liquor, ethanol can recycles, and chromite valuable element all utilizes, and three waste discharge is low, only has a small amount of solid slag.Energy consumption of the present invention is low, and pollute few, raw material availability is high, good in economic efficiency.
Wherein, chromite powder blowing air in slot electrode adds water Quick Oxidation, the acid-soluble compound producing chromium, magnesium, iron, aluminium, silicon, nickel under the condition of low chromite High Temperature High Pressure catalysis-oxygenant.The throw out magnesium hydroxide of chemosynthesis, aluminium hydroxide, Ferrox, silicon-dioxide remove solvable waterborne cation and negatively charged ion in electron ion film knot screen, above material of purifying.In the acid-soluble solution of chromite, six hydrated sulfuric acid chromium Crystallization Separation under the effect of vibration slaking salting-out agent, combines, designs ingenious, impart industrial value to low-grade chromite, meanwhile, and the recycle reached.
And add man-hour in chromite ore, adopt and the powder being less than 100 microns is placed in anodizing groove, anodizing trench bottom is blown into air, breeze adds quantitative water, makes breeze moist, makes the ferrous ion Quick Oxidation in ore be iron ion like this, make the lattice distortion of picotite, thus more thoroughly achieve acid-soluble, for technological design below provides guarantee, concrete acid-soluble effect is see table 1.
Table 1:1000g chromite composition and output
Adopt electron ion film knot screen to carry out removal of impurities to ion water-soluble in chemosynthesis throw out, ensure that the requirement that the low cost of the compounds such as Ferrox, white carbon black, magnesium hydroxide, aluminium hydroxide is purified.
This fully utilize project with serpentinite compared with, the advantage had
The main component of serpentinite is magnesium oxide, silicon oxide, ferric oxide, accounts for more than 90% of ore amount, nickel oxide about 0.2%, chromic oxide about 0.4%.Serpentinite utilizes and is mainly high-purity magnesium oxide for master, and Ferrox produced by silicon oxide production of silica white and ferric oxide; The industrial output of ore high purity magnesium oxide per ton, high-purity white carbon, high-purity oxalic acid ferrous iron is about 8000 yuan to 10000 yuan; Purify because do not have the application of ionic membrane knot screen of the present invention, high purity product per ton needs that high-purity pure water of 200 tons-500 tons rinses, cost large, waste is many.Again because high purity magnesium oxide compound domestic and international market scale is fire-retardant at the early-stage with other application market, market scale is little, so scope of the enterprise can not be too large, benefit is general.
The investment that the investment of the acid-soluble comprehensive utilization of chromite and serpentinite fully utilize approximately exceeds 5% to 10%.The main component of chromite is chromic oxide, ferric oxide, silicon oxide, magnesium oxide, aluminum oxide, nickel oxide, for the chromic oxide lower than industrial grade 25%; The all iron content of chromic oxide 25%, iron protoxide and ferric oxide 30%(chromite is much higher than serpentinite all iron content), magnesium oxide add silicon oxide, aluminum oxide be added about 40%.The industrial output of high-purity extract that chromite per ton is produced is about 15000 yuan to 18000 yuan; The market scale of chromated oxide and ferriferous oxide is very large, and product of the present invention is based on chromated oxide and ferriferous oxide, and magnalium Si oxide is auxiliary; So scope of the enterprise can be done greatly, intensivization development.
The present invention uses electron ion film knot screen, and good impurity removing effect, cost be low, it is little to waste; Be the powerful guarantee of the acid-soluble high purity oxide compound of chromite of the present invention, break Germany, the U.S., Japan in the technical superiority of high pure oxide, ensure that there is higher rate of return on investment in enterprise.
Accompanying drawing explanation
Fig. 1 is chromite ore work flow;
Fig. 2 is the acid-soluble work flow of chromite powder High Temperature High Pressure;
Fig. 3 is the reparation technology flow process of white carbon black;
Fig. 4 is Ferrox reparation technology flow process;
Fig. 5 is extraction six hydrated sulfuric acid chromium crystallization processes flow process;
Fig. 6 is the reparation technology flow process of magnesium hydroxide, aluminium hydroxide and nickelous sulfide;
Fig. 7 is the knot screen of chemical precipitates intermediate ion impurity of the present invention.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
embodiment 1:
A kind of ionic membrane knot screen, as shown in Figure 7, is characterized in that: comprise anolyte compartment 1, cathode compartment 2, supplies room 3, supplies room 3 between anolyte compartment 1 and cathode compartment 2,
Wherein,
Be provided with anode 11 in described anolyte compartment, and separated by anionic membrane 4 between supplies room;
Be provided with negative electrode 21 in described cathode compartment, and separated by cationic membrane 5 between supplies room;
Be provided with the material indigo plant 31 that solid insoluble is housed in described supplies room, bottom is provided with whipping appts 32.
Described anolyte compartment 1 is also provided with the first pure water inlet 12, first discard solution discharge port 13, first waste gas collection device 14; Described cathode compartment 2 is also provided with the second pure water inlet 22, second discard solution discharge port 23, Hydrogen collection device 24; Described supplies room is also provided with the 3rd pure water inlet 33, the 3rd discard solution discharge port 34, material main-inlet 35, discharge of materials mouth 36.
Described zwitterion film 4,5 is equipped with ionic membrane protection web plate 41,51;
Described material blue 31 is porous filter indigo plant;
Described whipping appts 32 adopts ultrasonic vibration agitator.
embodiment 2:
An impurity removal process for chemical precipitates intermediate ion impurity, is beneficial to above-mentioned device (as shown in Figure 7), comprises the steps:
1) before electrolysis: the material indigo plant 31 solid product produced in chemosynthesis being placed in supplies room, enough pure water are injected in anode room 1, cathode compartment 2 and supplies room 3, now, also soak full water in material basket, under agitation make the soluble ion being attached to solid product surface fully be dissolved in pure water;
2) electrolysis: under the effect of electrode, negatively charged ion is gas by anionic membrane at anode electrolysis, gas recovery, and positively charged ion is metal and basic metal or precipitation at negative electrode by electrolysis by cationic membrane, when negative electrode has hydrogen to produce, stops electrolysis;
3) after electrolysis: the liquid of first draining in two electrode vessels, and then the water in supplies room of draining, the soluble ion Impurity removal of chemical precipitates is complete.
embodiment 3:
The method of comprehensive utilization of chromite acid-soluble extraction valuable element ferrochrome silicon magnalium nickel, concrete technology step is as follows:
1) chromite ore processing (see accompanying drawing 1)
Be processed into through broken, ball milling the powder that granularity is less than 100 microns after chromite ore exploitation, be placed in anodizing groove, breeze adds water, makes breeze water tariff collection at 10wt%-15wt%, and make breeze moist, anodizing trench bottom is blown into air;
2) acid-soluble (see accompanying drawing 2)
Breeze is placed in high-temperature high-pressure reaction kettle and reacts with 50wt%-70wt% sulphuric acid soln, wherein, the amount adding sulfuric acid is: the mass ratio of breeze and sulfuric acid is 1:2 to 1:3, temperature of reaction kettle is 120 DEG C ~ 200 DEG C, pressure is at 0.5MPa ~ 1MPa, stirring velocity is that (amount according to anti-thing regulates 200-300 rev/min, optimum reaction condition is: the concentration of sulfuric acid is 60wt%, the mass ratio of breeze and sulfuric acid is 1:2.8, temperature of reaction kettle is 150 DEG C, pressure is at 0.8MPa, stirring velocity is 300 rev/min), catalysis-oxygenant (hydrogen peroxide or perchloric acid) is added in reaction, reaction times 1 is little of 12 hours, until make ferrous iron be oxidized to ferric iron completely,
3) solid-liquid separation
Use whizzer or film, molecular sieve filtration, solid-liquid is thoroughly separated;
4) the producing (see accompanying drawing 3) of white carbon black
After separation with silicon-dioxide be main component solid again ball milling slurrying react with strong acid in high-temperature high-pressure reaction kettle, the impurity in silicon-dioxide is fully reacted, by solid-liquid separation, liquid enter waste water operation carry out process Posterior circle utilize.Silica solid cleans through pure water, enters the removal of impurities of electron ion film knot screen.Silicon-dioxide after removal of impurities and sodium hydroxide solution react, with hydrothermal method high purity superfine white carbon black.The white carbon black produced enters the removal of impurities of electron ion film device again, and removal of impurities post-drying is packed.
5) heavyly ironly Ferrox (see accompanying drawing 4) is got
Liquid liquid after filtration adds hydrogen peroxide in settling bath makes a small amount of ferrous ion complete oxidation in liquid be iron ion, makes the ferrous sulfate complete oxidation in liquid be ferric sulfate; After testing without after ferrous ion in solution, detect the concentration of iron ion in solution, calculate after adding the amount of oxalic acid, add oxalic acid, oxalic ferrous precipitation, carry out solid-liquid separation, liquid enters next step link;
By isolated solid-state Ferrox after pure water cleaning, mix with pure water in electron ion film knot screen and carry out removal of impurities, obtain the oven dry of high-purity oxalic acid ferrous iron and pack;
6) six hydrated sulfuric acid chromium (see accompanying drawing 5) are extracted
Liquid after being separated in step 5) is the temperature of 15 ± 2 DEG C, add 99.5% ethanol for doing salting-out agent vibration slaking 24 hours, six hydrated sulfuric acid chromium crystallizations, solid-liquid centrifugation is separated, solid drying packaging is preserved, liquid fractionation by distillation ethanol, and ethanol reclaims and continues to utilize, liquid after separating alcohol enters next step link
Wherein, the amount that salting-out agent add is the 50wt%-80wt% of amount of liquid;
7) extraction (see accompanying drawing 6) of magnesium hydroxide and aluminium hydroxide
Add excessive sodium hydrate or ammonia soln in the liquid be separated in step 6), produce the mixing solutions of magnesium hydrate precipitate and sodium sulfate, sodium metaaluminate and Sodium chromate, filter and obtain magnesium hydroxide solid; After the cleaning of magnesium hydroxide solid pure water, in electron ion film knot screen after removal of impurities, obtain high purity magnesium hydroxide, drying is packed.
Add excess carbon dioxide gas in filtered fluid, obtain aluminum hydroxide precipitation, through solid-liquid separation, solid aluminum hydroxide is with after pure water cleaning, removal of impurities in electron ion film knot screen, more further with pure water cleaning, reach the requirement post-drying packaging of high purity product;
8) heavy nickel (see accompanying drawing 6)
Add sodium sulphite precipitated the sodium sulphite add-on that the content meter that adds nickel ion after testing in the solution after magnesium hydroxide and aluminium hydroxide calculates in step 7) after and generate nickel sulphide precipitation, after filtration, obtain nickelous sulfide;
9) filtrate process
The liquid obtained after step 8) is mainly sodium sulfate liquid, after crystallization, obtain sodium sulfate crystal
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (10)

1. an ionic membrane knot screen, is characterized in that: comprise anolyte compartment, cathode compartment, supplies room, supplies room between anolyte compartment and cathode compartment,
Wherein,
Be provided with anode in described anolyte compartment, and separated by anionic membrane between supplies room;
Be provided with negative electrode in described cathode compartment, and separated by cationic membrane between supplies room;
Be provided with the material that solid insoluble is housed in described supplies room blue, bottom is provided with whipping appts.
2. ionic membrane knot screen according to claim 1, is characterized in that: described anolyte compartment is also provided with the first pure water inlet, the first discard solution discharge port, the first waste gas collection device; Described cathode compartment is also provided with the second pure water inlet, the second discard solution discharge port, Hydrogen collection device; Described supplies room is also provided with the 3rd pure water inlet, the 3rd discard solution discharge port, material main-inlet, discharge of materials mouth.
3. ionic membrane knot screen according to claim 1 and 2, is characterized in that: described zwitterion film is equipped with ionic membrane protection web plate;
Preferably, described material is blue is porous filter indigo plant;
Preferred further, described whipping appts adopts ultrasonic vibration agitator.
4. an impurity removal process for chemical precipitates intermediate ion impurity, is characterized in that: be beneficial to the device described in any one of claims 1 to 3, comprise the steps:
1) before electrolysis: the material indigo plant solid product produced in chemosynthesis being placed in supplies room, inject enough pure water in anode room, cathode compartment and supplies room, under agitation make the soluble ion being attached to solid product surface fully be dissolved in pure water;
2) electrolysis: under the effect of electrode, negatively charged ion is gas by anionic membrane at anode electrolysis, gas recovery, and positively charged ion is metal and basic metal or precipitation at negative electrode by electrolysis by cationic membrane, when negative electrode has hydrogen to produce, stops electrolysis;
3) after electrolysis: the liquid of first draining in two electrode vessels, and then the water in supplies room of draining, the soluble ion Impurity removal of chemical precipitates is complete.
5. the method for comprehensive utilization of a chromite acid-soluble extraction valuable element ferrochrome silicon magnalium nickel, it is characterized in that: be first micro mist by chrome ore crushing grinding, micro mist blows atmospheric oxidation in anodizing pond, makes ferrous ions be iron ion, destroys picotite lattice; Chromite micro mist after oxidation in the reactor of high temperature, high pressure with sulfuric acid reaction, under the effect of oxidation-catalyzer, generating the mixing liquid of sulfur acid chromium, magnesium sulfate, Tai-Ace S 150, ferric sulfate and single nickel salt and silicon-dioxide and insoluble mineral is main throw out; By solid-liquid separation, solids is through obtained white carbon black of again purifying; The fractional extraction of liquid phase liquid goes out six water chromium sulphates, high purity magnesium hydroxide, high purity aluminium hydroxide, high-purity oxalic acid ferrous iron, nickelous sulfide.
6. the method for comprehensive utilization of chromite according to claim 5 acid-soluble extraction valuable element ferrochrome silicon magnalium nickel, is characterized in that: concrete technology step is as follows:
1) chromite ore processing
Be processed into through broken, ball milling the powder that granularity is less than 100 microns after chromite ore exploitation, be placed in anodizing groove, breeze adds water, and anodizing trench bottom is blown into air; Anodizing groove works, and makes breeze Quick Oxidation;
Breeze picotite lattice after oxidation is destroyed, and is easier to follow-up acid dissolution;
2) acid-soluble
Breeze is placed in high-temperature high-pressure reaction kettle and reacts with sulphuric acid soln, adds catalysis-oxygenant in reaction, and the reaction times is 1 little of 12 hours;
3) solid-liquid separation
Use whizzer or film, molecular sieve filtration, solid-liquid is thoroughly separated;
4) the producing of white carbon black
After separation with silicon-dioxide be main component solid again ball milling slurrying react with strong acid in high-temperature high-pressure reaction kettle, the impurity in silicon-dioxide is fully reacted, by solid-liquid separation, liquid enter waste water operation carry out process Posterior circle utilize;
Silica solid cleans through pure water, enters the electron ion film knot screen removal of impurities described in any one of claim 1 to 3; Silicon-dioxide after removal of impurities and sodium hydroxide solution react, with hydrothermal method high purity superfine white carbon black;
The white carbon black produced enters the removal of impurities of electron ion film device again, and removal of impurities post-drying is packed;
5) heavyly ironly Ferrox is got
Liquid liquid after filtration adds hydrogen peroxide in settling bath makes a small amount of ferrous ion complete oxidation in liquid be iron ion, makes the ferrous sulfate complete oxidation in liquid be ferric sulfate; After testing without after ferrous ion in solution, detect the concentration of iron ion in solution, calculate after adding the amount of oxalic acid, add oxalic acid, oxalic ferrous precipitation, carry out solid-liquid separation, liquid enters next step link;
By isolated solid-state Ferrox after pure water cleaning, mix with pure water in the electron ion film knot screen described in any one of claims 1 to 3 and carry out removal of impurities, obtain the oven dry of high-purity oxalic acid ferrous iron and pack;
6) six hydrated sulfuric acid chromium are extracted
Liquid after being separated in step 5), the temperature of 15 ± 2 DEG C, adds salting-out agent vibration slaking 24 hours, six hydrated sulfuric acid chromium crystallizations, solid-liquid centrifugation is separated, and solid drying packaging is preserved, liquid fractionation by distillation ethanol, ethanol reclaims and continues to utilize, and the liquid after separating alcohol enters next step link;
7) extraction of magnesium hydroxide and aluminium hydroxide
Add excessive sodium hydrate or ammonia soln in the liquid be separated in step 6), produce the mixing solutions of magnesium hydrate precipitate and sodium sulfate, sodium metaaluminate and Sodium chromate, filter and obtain magnesium hydroxide solid; After the cleaning of magnesium hydroxide solid pure water, in the electron ion film knot screen described in any one of claims 1 to 3 after removal of impurities, obtain high purity magnesium hydroxide, drying is packed;
Excess carbon dioxide gas is added in filtered fluid, obtain aluminum hydroxide precipitation, through solid-liquid separation, solid aluminum hydroxide is with after pure water cleaning, removal of impurities in the electron ion film knot screen described in any one of claims 1 to 3, again further with pure water cleaning, reach the requirement post-drying packaging of high purity product;
8) heavy nickel
Add sodium sulphite precipitated the sodium sulphite add-on that the content meter that adds nickel ion after testing in the solution after magnesium hydroxide and aluminium hydroxide calculates in step 7) after and generate nickel sulphide precipitation, after filtration, obtain nickelous sulfide;
9) filtrate process
The liquid obtained after step 8) is mainly sodium sulfate liquid, after crystallization, obtain sodium sulfate crystal.
7. the method for comprehensive utilization of chromite according to claim 6 acid-soluble extraction valuable element ferrochrome silicon magnalium nickel, is characterized in that: in described step 1), adds water and makes breeze water tariff collection at 10wt%-15wt%.
8. the method for comprehensive utilization of chromite according to claim 6 acid-soluble extraction valuable element ferrochrome silicon magnalium nickel, it is characterized in that: described step 2) in, temperature of reaction kettle is 120 DEG C ~ 200 DEG C, pressure is 200-300 rev/min in 0.5MPa ~ 1MPa, stirring velocity;
Preferably, temperature of reaction kettle is 150 DEG C, pressure is 300 rev/min in 0.8MPa, stirring velocity.
9. the method for comprehensive utilization of chromite according to claim 6 acid-soluble extraction valuable element ferrochrome silicon magnalium nickel, is characterized in that: described step 2) in, the concentration of sulfuric acid is 50wt%-70wt%, and the mass ratio of breeze and sulfuric acid is 1:2 to 1:3;
Preferably, the concentration of sulfuric acid is 60wt%, and the mass ratio of breeze and sulfuric acid is 1:2.8;
Preferably, described step 2) in, described catalysis-oxygenant adopts hydrogen peroxide or perchloric acid, makes ferrous iron be oxidized to ferric iron completely.
10. the method for comprehensive utilization of chromite according to claim 6 acid-soluble extraction valuable element ferrochrome silicon magnalium nickel, it is characterized in that: in described step 6), described salting-out agent are the ethanol of more than 99.5%, and the amount added is the 50wt%-80wt% of amount of liquid.
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