CN107055502A - The method that water-soluble combination alkali soluble extracts carbon from electrolytic cell waste cathode carbon block - Google Patents
The method that water-soluble combination alkali soluble extracts carbon from electrolytic cell waste cathode carbon block Download PDFInfo
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Abstract
The invention discloses a kind of method that water-soluble combination alkali soluble extracts carbon from electrolytic cell waste cathode carbon block, this method is first to carry out ore grinding, then carry out it is water-soluble go out, alkali leaching is carried out with NaOH to the water-soluble slag that obtains under the conditions of water-soluble.By technical scheme, the carbon content in electrolytic cell waste cathode carbon block, from 65% or so, can be promoted to 90% or so, so as to realize the recycling to carbon in electrolytic cell waste cathode carbon block.
Description
Technical field
The present invention relates to electrolytic cell waste cathode carbon block technical field of comprehensive utilization, and in particular to a kind of water-soluble combination alkali soluble from
The method that carbon is extracted in electrolytic cell waste cathode carbon block.
Background technology
Aluminium cell typically needs to carry out large repairs after using 4 to 5 years, and the average groove life of majority enterprise of China was on 1500 days left sides
The right side, removes substantial amounts of waste cathode carbon block during overhaul.In the prior art, the processing method to waste cathode of aluminum electrolytic cell carbon block is mainly
Lime is added in waste cathode carbon block to be allowed to react with electrolyte therein, is obtained calcirm-fluoride, sodium fluoride and aluminum fluoride, is made
Fluorine obtains solidifying to re-use, and the charcoal of recovery is reused for manufacturing cathode material, but processing cost is too high.Or utilize cement
Kiln internal reaction temperature is high, the carbon block condition such as residence time length on stream, makes the harmful substance in waste cathode carbon block in height
Decomposition displacement is carried out in warm environment, and is finally solidificated in clinker, while the carbon in waste cathode carbon block is reduced as fuel
The consumption of coal.But, using the shortcoming of this method, also clearly fluorine has infringement to refractory brick, and fluorine is easily arranged with flue gas
It is put into air and causes atmosphere pollution；The content of sodium is high in waste cathode carbon block, can have an impact to cement later strength.
Chinese patent literature Publication No. 105586607A, a kind of entitled patent Shen of the Application way of waste cathode carbon block
Please file provide the technical scheme that utilizes of such a waste cathode carbon block, it is that aluminium cell overhaul is stopped into plow using process
The waste cathode carbon block removed, carries out coarse crushing, in small, broken bits, screening, sorting, obtains carbon particles and electrolyte granular in waste cathode carbon block,
Carbon particles therein return to aluminum electrolysis process for aluminium cathode carbon pieces raw materials for production, electrolyte granular.
Chinese patent literature Publication No. 101798691A, a kind of entitled method for reclaiming waste cathode of aluminum electrolytic cell it is special
Sharp application documents provide such technical scheme, comprise the following steps:1) fire proofed wood of waste cathode carbon block surfaces stick is cleared up
Material, insulation material；2) waste cathode carbon block is broken into 1~6mm particle；3) using the waste cathode carbon block particle after above-mentioned crush
Prebake is carried out to the electrolytic cell after overhaul by coke grain calcination startup method；4) residual particles after prebake are reclaimed；5) separating residual
Ash content in particle；6) residual particles of recovery are returned into aluminium cell as fluoride salt to use.
Chinese patent literature Publication No. 101440500, the place for the waste cathode carbon block that entitled electrolytic aluminium overhaul groove is produced
Put method and provide such technical scheme：It is that electrolytic cell overhaul is produced to the waste cathode carbon block machine sorted out in waste residue
Tool is broken into after powder, is added in alumina producer sintering process system and is carried out dispensing, is then entered together with raw slurry and is burnt till workshop
Clinkersintering is carried out in rotary kiln.
But research has shown that, waste cathode carbon block waste residue carbon element content is higher, can reach 66.07%, other elements
In it is higher with fluorine, sodium, aluminium content, be the major impurity of the waste residue, cyanogen root content therein reaches 8.7ppm, beyond country row
Put standard.Therefore, the recycling to waste cathode carbon block waste residue is the recovery of carbon.But prior art disclosed above,
The recovery to carbon in the negative electrode that gives up does not propose preferable technical scheme.
The content of the invention
The invention provides a kind of method that water-soluble combination alkali soluble extracts carbon from electrolytic cell waste cathode carbon block, to solve electricity
Solve the problem of complex utilization of groove waste cathode carbon block.
The invention provides following technical scheme：
A kind of method that water-soluble combination alkali soluble extracts carbon from electrolytic cell waste cathode carbon block, this method is first to carry out ore grinding,
Then carry out it is water-soluble go out, alkali leaching is carried out with NaOH to the water-soluble slag that obtains under the conditions of water-soluble.
Wherein, mog is -200 mesh during ore grinding, and collecting agent uses diesel oil, and foaming agent uses 2#Oil, inhibitor is used
Waterglass.The water dissolving-out process condition is：Liquid-solid ratio 2-4:1st, 18-25 DEG C of temperature, time 50-80min.The alkali leaches work
Skill condition is：Liquid-solid ratio 3-5:1st, 40-60 DEG C of temperature, time 50-70min, NaOH consumption 160-185g/L.
It is preferred that, the slag phase sampling after can also being leached again to alkali carries out Ore Leaching with hydrochloric acid or sulfuric acid, finally carries out carbon
The detection of content.
The scheme of two kinds of extraction carbon is provided respectively using hydrochloric acid and sulfuric acid leaching here：
The first scheme, first using water-soluble, it is water-soluble go out optimum process condition：Liquid-solid ratio 3:1st, 20 DEG C of temperature, time
60min；Alkali soluble is carried out after water-soluble, alkali leaches optimum process condition：Liquid-solid ratio 4:1st, temperature 50 C, time 60min, NaOH consumption
175g/L；Then sour molten, hydrochloric acid Ore Leaching optimum process condition is carried out using hydrochloric acid：HCl (concentration 37%):H2O=3:1st, liquid
Gu ratio=3:1st, 80 DEG C of temperature, time 60min；Detect that carbon content can reach 89.9% after dissolution.
Second scheme, first using water-soluble, it is water-soluble go out optimum process condition：Liquid-solid ratio 3:1st, 20 DEG C of temperature, time
60min；Alkali soluble is carried out after water-soluble, alkali leaches optimum process condition：Liquid-solid ratio 4:1st, temperature 50 C, time 60min, NaOH are used
175g/L；Then sour molten, sulfuric acid leaching optimum process condition is carried out using sulphur：H2SO4(concentration 98%):H2O=3:1st, liquid-solid ratio
=3:1st, 80 DEG C of temperature, time 60min；Detect that carbon content can reach 90% after dissolution.
The beneficial effect that the present invention reaches：, can be by electrolytic cell waste cathode carbon block by technical scheme
Carbon content, from 65% or so, is promoted to 90% or so, so as to realize the recycling to carbon in electrolytic cell waste cathode carbon block.
Brief description of the drawings
Fig. 1 is waste cathode carbon block XRD spectra；
The beneficiating method that Fig. 2 is the present invention extracts carbon process chart；
Fig. 3 is water-soluble rear product X RD thing phasors；
Fig. 4 is the thing phase composition schematic diagram of product after sulfuric acid dissolution；
Fig. 5 is solids phase and relative amount schematic diagram after hydrochloric acid dissolution.
Embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.Have in the present invention and following examples
Quantity number, percentage, quantitative proportion etc. are closed, if without specified otherwise, referring both to mass unit.
First, use XRD technologies of the invention determine the existing forms of each element in waste cathode carbon block, and the waste residue is carried out
XRD analysis, its spectrogram is as shown in Figure 1.It can be drawn from the XRD spectra of former state, main sweat has carbon, sodium fluoride, six in the sample
Cryolite, eutectic aluminum na oxide, eutectic ferrisodium cyanide and calcirm-fluoride.
By understanding that in waste cathode carbon block, NaF content accounts for 12%, C content to the analysis of each phase content of waste residue
The content for accounting for 66%, Na4Fe (CN) 6 accounts for 2%, NaAl11O17 content and accounts for 3%, Al2Na6F12 content and account for
16%, CaF2 content account for 16%.
The present invention realizes by the experiment of following examples and extracts carbon from above-mentioned waste cathode carbon block.
Embodiment 1：Electrolytic cell waste cathode carbon block grindability
Bond work index is determined：As requested, experiment determines the mesh of raw ore -200 (0.074mm) Bond work index first.Mill
Ore deposit circulating load presses 250%, it is contemplated that undersize quality is 237g.Result of the test is listed in table 1.
1 raw ore of table -200 mesh (0.074mm) Bond work index determination test result
Explanation：Gbp is every turn of net generation -0.074mm product quality in table, similarly hereinafter.
Experiment is carried out after one group, it is found that this ore grinding Gbp values are substantially less than normal relative to testing in the past, and the second of calculating
Secondary mill speed needs 1396 turns, much larger than the normal level of general ore.Think, because raw ore hardly possible is ground, and raw ore particulate
Product can play a part of resistance mill among ore grinding, huge to dry grinding interference, cause remaining after ore grinding is carried out to a certain extent
Coarse grain product is difficult to further levigate.In view of the above results, experiment considers purpose product granularity being adjusted to -100 mesh
(0.15mm), then Bond work index measure is carried out, result of the test is listed in table 2.
2 raw ore of table -100 mesh (0.15mm) Bond work index determination test result
From the result of the test of table 2, after purpose mog is adjusted, experiment Gbp values, which are appointed, is so much smaller than normal value, and
Drastically reduced with the increase of ore grinding revolution.When experiment proceeds to the 3rd group, it is 6838 turns to calculate grinding machine revolution, according to conventional examination
Experience is tested, it is much larger than normal value.Result of the test is analyzed, experiment thinks the ore deposit among dry milled process, with prolonging for ore grinding time
Long, it is understood that there may be the situation that grinding efficiency is drastically reduced, for this, experiment has carried out checking test, and experiment is using ore grinding revolution as change
Amount, using -200 mesh product yields as criterion, result of the test is listed in table 3.
The ore grinding checking test result of table 3
It can be seen from the result of table 3 under identical condition, grinding machine revolution increases to 300 turns, the production of -200 mesh from 100 turns
Product amount increase only 0.2g, can be ignored in pilot system error, i.e., gone to from 100 between 300 turns, grinding machine ore grinding effect
Rate is zero.
Embodiment 2：Beneficiating method extracts carbon
Experiment has carried out the experiment of flotation desk study to aluminium electroloysis waste cathode carbon block raw ore, investigates the optional performance of raw ore.
The multielement analysis of raw ore is shown, raw ore solid (fixed carbon) containing C is 67.83%, and raw ore water soluble salt content is higher, through experiment
It is 9.60% to determine its content.
To explore the optional performance of the ore deposit, experiment has carried out preliminary flotation collector and foaming agent condition test, suppressed
Agent and regulator condition test and mog condition test, technological process are as shown in Figure 2.
1) collecting agent and foaming agent condition test
Graphite flotation is often kerosene, diesel oil etc. with collecting agent, and it is 2# oil, 4# oil etc. to commonly use foaming agent.The bar of the present embodiment
Part experiment is carried out in mog in -200 mesh 90% or so, and collecting agent and foaming agent mainly use graphite flotation conventional dose
(wherein 98# oil is floatation frother, and its frothing capacity is better than 2# oil, and with certain collecting performance).
2) inhibitor and regulator condition test
Graphite flotation often has lime, sodium carbonate, waterglass etc. with inhibitor and regulator, and this experiment raw ore contains necessarily
The pyrite of amount, addition lime is favorably improved the inhibition to pyrite.This inhibitor and regulator condition test are adopted
Medicament is often used with graphite flotation, other experimental conditions are：The mesh of mog -200 90%, collecting agent are selected from diesel oil, foaming agent
With 2# oil.
Raw ore is tested in alkalescence, in the case of without any medicament, pH values of pulp can reach 9~10, and experiment shows
Pyrite under the conditions of this in raw ore is smaller to graphite influence of flotation, and flotation froth viscosity is improved after addition lime, is caused selected
It is difficult；Appropriate addition waterglass helps to improve ore pulp dispersive property, and has certain inhibition to gangue, is conducive to improving
Flotation efficiency.
3) mog condition test
This raw ore is amorphous graphite ore deposit, and the type ore graphite and the embedding cloth relation of gangue mineral are complicated, and flotation is difficult,
Therefore suitable mog is selected to ensure ore grinding liberation degree of minerals, it is larger to the influence of flotation of the ore deposit.For this, experiment is carried out
One group of mog condition test, other experimental conditions are：Inhibitor is selected from waterglass, collecting agent from diesel oil, foaming agent
With 2# oil.
Result of the test illustrates that raw ore flotation separating effect is poor under thicker mog, reach in mog-
After 200 mesh 100%, flotation effect makes moderate progress.
4) conclusion
The waste cathode of aluminum electrolytic cell carbon block raw ore that the present embodiment is used is amorphous graphite, and head grade is higher but washability
It is poor.Flotation exploratory experiment to raw ore shows, carries out flotation to raw ore, concentrate grade can be improved to a certain extent.But
Under conventional mog and regime of agent, the sorting index of acquisition is relatively less preferable.
Embodiment 3：Sour dissolving-out process extracts carbon
1) it is water-soluble go out experimental result
In test, the parameters such as liquid-solid ratio, temperature, time, grain diameter are mainly investigated in electrolytic cell waste cathode carbon block
Si, F, Al and C element dissolution rate.Water-soluble rear product X RD things phasor is as shown in figure 3, water-soluble rear product X RD things phase table is as follows
Shown in table 5.
The water-soluble rear product X RD things phase table of table 5
It is a discovery of the invention that in process in leaching, each factor influences larger, the main dissolution of process section to the dissolution rate of sodium fluoride
Thing is sodium fluoride.In process in leaching, each factor to carbon, hexafluoro sodium aluminate, eutectic aluminum na oxide, eutectic ferrisodium cyanide with
And the dissolution rate of calcirm-fluoride influences smaller, the not dissolution substantially in process section.
2) sulfuric acid dissolution experimental result
The experiment of single factor of residual acid dissolution has been completed on the basis of preliminary experiment is explored, the use of acid is mainly completed
Amount, liquid-solid ratio, leaching temperature, dissolution time, the influence to the result of extraction of each element in slag；The thing phase of product after sulfuric acid dissolution
Composition is as shown in Figure 4.
Present invention discover that in sulfuric acid process in leaching, each factor to it is water-soluble go out rear slag in hexafluoro sodium aluminate dissolution rate shadow
Sound is larger, and the main leachable of process section is hexafluoro sodium aluminate.
In process in leaching, each factor is to carbon, eutectic aluminum na oxide, eutectic ferrisodium cyanide and calcirm-fluoride sodium fluoride
Dissolution rate influence smaller, the not dissolution substantially in process section.
3) hydrochloric acid dissolution experimental result
The present embodiment hydrochloric acid dissolution experiment uses following process conditions：Concentration is 30%HCl dissolutions, solid-to-liquid ratio 1：3,
80 DEG C of temperature, time 1h.
Result of implementation：Sample loss of weight is 17.3%, and carbon content is 90.4%.
Meanwhile, the present embodiment has carried out Discriminating materials to the solid product of hydrochloric acid dissolution, as a result such as Fig. 5 and table 6 below：
Solids phase table after the hydrochloric acid dissolution of table 6
Present invention discover that in hydrochloric acid process in leaching, each factor to it is water-soluble go out rear slag in hexafluoro sodium aluminate dissolution rate shadow
Sound is larger, and the main leachable of process section is hexafluoro sodium aluminate.Secondly, the partially fluorinated calcium of hydrochloric acid dissolution energy dissolution.
In process in leaching, dissolution of each factor to carbon, eutectic aluminum na oxide, eutectic ferrisodium cyanide and sodium fluoride
Rate influences smaller, the not dissolution substantially in process section.
4) sulfuric acid dissolution Orthogonal experiment results
It is as shown in table 7 below：
The sulfuric acid dissolution Orthogonal experiment results table of table 7
In terms of Orthogonal experiment results, experimental repeatability is preferable, at optimum conditions, after washing and sulfuric acid dissolution, carbon
Content can have the 66% of former state to bring up to 89.62%.
Embodiment 4：Alkali dissolving-out process extracts carbon
The present invention extracts carbon using alkali dissolving-out process, and being based on the discovery that in electrolytic cell waste cathode carbon block has content higher
Electrolyte Na3AlF6, being leached by alkali can be such that it is dissolved into leachate, reach that it departs from solid mixture, make mixture
Composition tails off, and reaches the purpose that carbon ratio example is improved.
It is respectively 3 that the present embodiment, which explores liquid-solid ratio,：1、4:1、5:1、6:When 1, the dissolution quality of each element, and electrolysis
The content of carbon in groove waste cathode carbon block.Experimental implementation is 175g/L in NaOH consumptions, and extraction time is 60min, and extraction temperature is
Carried out under conditions of 50 DEG C, fetch water molten optimum condition dissolution slag specimen 10g, control liquid-solid ratio is respectively 3:1、4:1、5:1 and 6:1,
Then dissolution experiment is carried out.Dissolution terminate after to the dissolution quality of the elements such as Al, Si, Fe, F, C, and electrolytic cell waste cathode carbon
The content of carbon measures analysis in block.
We can find out the optimal dissolution liquid-solid ratio of each element respectively.I.e. the optimal dissolution solid-to-liquid ratio of F elements is 4:1；
In experiment solid-to-liquid ratio excursion, the optimal dissolution solid-to-liquid ratio of Si elements is the bigger the better；The optimal dissolution liquid-solid ratio of Al elements
For 5:1；The optimal dissolution liquid-solid ratio of Fe elements is 5:1.
And the content of each element in the slag phase after alkali leaching, after analyzing after testing, for example following each table of concrete outcome：
The liquid-solid ratio of table 8 be 3: 1 when slag phase in each element content and dissolution rate
The liquid-solid ratio of table 9 be 4: 1 when slag phase in each element content and dissolution rate
The liquid-solid ratio of table 10 be 5: 1 when slag phase in each element content and dissolution rate
The liquid-solid ratio of table 11 be 6: 1 when slag phase in each element content and dissolution rate
Table 8 retains content to what table 11 indicated each element in slag phase, it can be seen that the leaching effect that alkali is leached.Cause
The content of Si, Fe element is integrally relatively low in slag phase, therefore it may be concluded that aqueous slkali can be removed preferably in slag phase
Si, Fe element, so as to improve the content of carbon in electrolytic cell waste cathode carbon block.Meanwhile, the data in each table are contrasted, can be accurate
To the optimal liquid-solid ratio of each element.
The experiment of the present embodiment also found that the weight-loss ratio of alkali leaching sample ore is presented with the increase of liquid-solid ratio first to be increased, solid in liquid
The trend tended towards stability after than 4: 1.In addition, carbon content is presented with the increase of liquid-solid ratio first reduces the trend for increasing reduce again afterwards,
Occur optimum value in liquid-solid ratio excursion, when liquid-solid ratio is 5: 1, carbon content reaches maximum, be 83.44%.And it is different
Under liquid-solid ratio, less, excursion is in 1.4%, therefore influence of the liquid-solid ratio to carbon content is little for the change of carbon content.
The present embodiment using it is optimal it is water-soluble under the conditions of dissolution slag specimen for the alkali leaching experiment under sample progress different temperatures.Take
Water-soluble optimum condition dissolution slag specimen 10g, is 4 in liquid-solid ratio:1st, extraction time is the experiment condition that 1h, NaOH concentration are 300g/L
Under, examine or check the content of carbon in electrolytic cell waste cathode carbon block under different extraction temperatures (25 DEG C, 30 DEG C, 40 DEG C, 50 DEG C and 100 DEG C).
After experiment terminates, the content of each element in alkali leaching liquor has been carried out detection and analysis, the present embodiment finds,
In the range of experimental temperature, the concentration of Si, Al, Fe element is as increased trend (Al members after first reduction are presented in the increase of temperature
The dissolution concentration of element decreases again after increase), and be at ambient temperature, i.e., there is higher leach when temperature is 25 DEG C
Concentration, therefore the optimal leaching temperature of Si, Al, Fe element is 25 DEG C.Wherein, the dissolution concentration of F elements is presented first with temperature increase
Increase the variation tendency then reduced after reduction, optimal leaching temperature is reached when temperature is 50 DEG C.
The content of each element in slag phase in experimental analysis after the same leaching to alkali is detected and analyzed, specifically
As a result such as following each table：
The temperature of table 12 be 25 DEG C when slag phase in each element content and dissolution rate
The temperature of table 13 be 30 DEG C when slag phase in each element content and dissolution rate
The temperature of table 14 be 40 DEG C when slag phase in each element content and dissolution rate
The temperature of table 15 be 50 DEG C when slag phase in each element content and dissolution rate
The temperature of table 16 be 100 DEG C when slag phase in each element content and dissolution rate
It was found from table 12 to table 16, the content of each element in alkali is leached under each temperature conditionss leaching effect and slag phase.
The content of each element can be compared at the same temperature simultaneously, show which kind of element is more easy to remove from sample ore at this temperature
Go.During such as 25 DEG C as seen from the table, 40 DEG C with 100 DEG C, Fe elements are more easy to leach.
Finally, aggregate analysis is carried out to experimental result, it is found that the weight-loss ratio of laboratory sample is with temperature under experimental conditions
Though increase has local fluctuation, the overall ever-increasing trend of presentation, and temperature are higher, and the soluble impurity in sample is got over
It is soluble in alkaline leaching liquid.The main cause for this phenomenon occur is that high temperature is conducive to improving reaction rate constant, is promoted anti-
The progress answered.Meanwhile, with being continuously increased for extraction temperature, increased trend is totally presented in the content of carbon in alkali leaching sample ore, this
After being removed mainly due to the soluble impurity in sample ore, sample ore oeverall quality declines, and denominator diminishes, so that carbon content is improved.
The present embodiment for it is optimal it is water-soluble under the conditions of dissolution slag specimen carried out the exploratory experiment of extraction time.Test operation
It in NaOH consumptions is that 175g/L, liquid-solid ratio are that 4: 1, temperature is to carry out under conditions of 50 DEG C to be, molten optimum condition dissolution slag of fetching water
Sample 10g, examines or check the content of carbon in electrolytic cell waste cathode carbon block under different extraction times (45min, 60min and 90min).Experiment knot
Shu Hou, leachate is separated by filtration with slag phase, the filter cake quality after record filtrate volume and drying, is then analyzed.
The present embodiment finds that the concentration of F, Si, Al element in leachate under different extraction times there is identical to change
Trend, is as the trend reduced after existing increase is presented in the increase of temperature, i.e., to have when extraction time is 60min maximum molten
Go out concentration；In addition, the concentration of Fe elements and F, Si, Al change in concentration trend contrast in leachate, with extraction time
Increase, the leaching concentration of Fe elements is first reduced to be increased afterwards, is reached in 60min minimum, and in scope of experiment, Fe elements most preferably soak
Go out the time for 40min.
The content of each element in slag phase in experimental analysis after the same leaching to alkali is detected and analyzed, specifically
As a result such as following each table：
The time of table 17 be 45min when slag phase in each element content and dissolution rate
The time of table 18 be 60min when slag phase in each element content and dissolution rate
The time of table 19 be 90min when slag phase in each element content and dissolution rate
It was found from table 17 to table 19, each element contains in alkali is leached under the conditions of each extraction time leaching effect and slag phase
Amount.The content of each element can be compared under same extraction time simultaneously, show which kind of element is more easy to from ore deposit at this temperature
Removed in sample.As seen from the table, when extraction time is 60min and 90min, under identical extraction time, Fe elements most easily soak
Go out, and F elements are most difficult to leach；When extraction time is 45min, Si elements are easier to leach, and F elements are difficult to leach.
The present embodiment also found, with the increase of extraction time, and increase tendency is totally presented in the weight-loss ratio of alkali leaching sample ore,
In the range of the given extraction time of experiment, extraction time is longer, and the weight-loss ratio of alkali leaching sample ore is bigger, you can the removal of solubility impurity
More thorough, the reason for this show occur is probably the extension due to the reaction time so that reaction is more fully carried out.Separately
Outside, it has also been found that, carbon content in alkali leaching sample ore is with the same trend that overall increase is presented of the increase of extraction time, i.e.,
Time is longer, and carbon content is higher.
It is soluble when the present embodiment also explores base amount for 100g/L, 125g/L, 150g/L, 175g/L and 300g/L
The content of carbon in the removal situation and electrolytic cell waste cathode carbon block of impurity.Fetch water molten optimum condition dissolution slag specimen 10g, in liquid-solid ratio
For 4:1st, under the experiment condition that extraction time is 60min, extraction temperature is 50 DEG C, different base amounts are examined or check to the useless negative electrode of electrolytic cell
The influence of the content of carbon in carbon block.
After off-test, leachate is separated by filtration with slag phase, the filter cake quality after record filtrate volume and drying, then
Analyzed.
The present embodiment is found, in the range of experiment base amount, and the concentration of F ion is presented with the increase of base amount in dissolution fluid
First reduce increases the trend reduced again afterwards, has maximum dissolution concentration when base amount is 100g/l；Si ions in dissolution fluid
Concentration presents first to reduce to increase afterwards with the increase of base amount reduces the broken line trend being further added by again, is reached when base amount is 300g/l
To maximum dissolution concentration；Increased trend after first reduction is presented with the increase of base amount in the concentration of Al ions in dissolution fluid, that is, exists
Base amount reaches maximum dissolution concentration when being 300g/l；In addition, the concentration of Fe ions is presented with the increase of base amount in dissolution fluid
First increase the trend for dropping increase again afterwards, base amount reaches maximum dissolution concentration when being 300g/l.
The content of each element in slag phase in experimental analysis after the same leaching to alkali is detected and analyzed, specifically
As a result such as following each table：
The base amount of table 20 be 100g/L when slag phase in each element content and dissolution rate
The base amount of table 21 be 125g/L when slag phase in each element content and dissolution rate
The base amount of table 22 be 150g/L when slag phase in each element content and dissolution rate
The base amount of table 23 be 175g/L when slag phase in each element content and dissolution rate
The base amount of table 24 be 300g/L when slag phase in each element content and dissolution rate
It was found from table 20 to table 24, the content of each element in the leaching slag phase that alkali is leached under the conditions of different base amounts.Simultaneously
The content of each element can be compared under same base amount, show which kind of element is more easy to remove from sample ore under this base amount
Go.As when base amount removes 300g/l as seen from the table, i.e., Fe elements are more easy to leach under low base amount.Al dissolutions under 300g/l
Rate is 100%, and this data is insincere, it may be possible to because experimental error is caused.
Finally, aggregate analysis is carried out to experimental result, it is found that with the increase of base amount, laboratory sample alkali soaks subtracting for sample ore
Take the lead in increasing after reduction again, in the range of the given base amount of experiment, base amount is bigger, the weight-loss ratio of alkali leaching sample ore is bigger, i.e.,
The removal of soluble impurity is more thorough.The present embodiment also found that the carbon content in alkali leaching sample ore is presented first with the increase of base amount
The trend increased after reduction, i.e. base amount are bigger, and carbon content is higher.
The present embodiment is more accurately to understand optimal leaching condition combination, entered again after experiment of single factor research is carried out
The orthogonal experiments of three factor ternaries is gone.Specific experiment condition and experimental data are as shown in Table 25：
The orthogonal experiment condition of table 25 and experimental data table
It was found from the experimental data shown from table 25, under B9 experiment conditions, i.e., liquid-solid ratio is 4: 1, and temperature is 100 DEG C, alkali
When consumption is 12ml, the content of carbon is maximum in electrolytic cell waste cathode carbon block, can reach 88.8865%.
Embodiment 5：Supplement experiment
The phase has carried out supplement experiment to the present embodiment again after the test, and to it is optimal it is water-soluble under the conditions of obtained water-soluble slag sample
Carry out alkali under optimal alkali leaching condition to leach, the slag phase sampling after then again leaching alkali is respectively with hydrochloric acid and sulfuric acid in optimal acid
Ore Leaching is carried out under the conditions of leaching, the detection of carbon content is finally carried out.Specific experiment data such as following table：
The dissolution quality (g) of each element under the conditions of different acid are molten after the water-soluble alkali soluble of table 26
Table 26 is the dissolution quality of each element under two groups of experiment conditions, and at the same time also carbon content is measured and divided
Analysis, it is as a result as follows：
1) water-soluble (condition：Liquid-solid ratio 3: 1,20 DEG C of temperature, time 60min) → alkali soluble (condition：Liquid-solid ratio 4: 1, temperature 50
DEG C, time 60min, NaOH 175g/L) → molten (condition of acid：HCl (concentration 37%)：H2O=3: 1, liquid-solid ratio=3:1st, temperature
80 DEG C, time 60min) → carbon content be 89.9%.
2) water-soluble (condition：Liquid-solid ratio 3:1st, 20 DEG C of temperature, time 60min) → alkali soluble (condition：Liquid-solid ratio 4:1st, temperature 50
DEG C, time 60min, NaOH consumption 175g/L) → molten (condition of acid：H2SO4 (concentration 98%):H2O=3:1st, liquid-solid ratio=3:1、
80 DEG C of temperature, time 60min) → carbon content be 90%.
Certainly, it is the concrete application example of the present invention above, the present invention also has other embodiments, all using equivalent
Replacement or the technical scheme of equivalent transformation formation, all fall within protection domain of the presently claimed invention.
Claims (4)
1. a kind of method that water-soluble combination alkali soluble extracts carbon from electrolytic cell waste cathode carbon block, it is characterised in that：This method is first
Carry out ore grinding, then carry out it is water-soluble go out, alkali leaching is carried out with NaOH to the water-soluble slag that obtains under the conditions of water-soluble.
2. water-soluble combination alkali soluble according to claim 1 extracts the method for carbon, its feature from electrolytic cell waste cathode carbon block
It is：Mog is -200 mesh during the ore grinding, and collecting agent uses diesel oil, and foaming agent uses 2#Oil, inhibitor uses water glass
Glass.
3. water-soluble combination alkali soluble according to claim 1 extracts the method for carbon, its feature from electrolytic cell waste cathode carbon block
It is：The water dissolving-out process condition is：Liquid-solid ratio 2-4:1st, 18-25 DEG C of temperature, time 50-80min.
4. water-soluble combination alkali soluble according to claim 1 extracts the method for carbon, its feature from electrolytic cell waste cathode carbon block
It is：The alkali extract technology condition is：Liquid-solid ratio 3-5:1st, 40-60 DEG C of temperature, time 50-70min, NaOH consumption 160-
185g/L。
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| US20020114748A1 (en) * | 1999-12-17 | 2002-08-22 | Vijaya Kasireddy | Recycling of spent pot linings |
| CN102146570A (en) * | 2011-02-26 | 2011-08-10 | 王建军 | Method for producing aluminum anode by using waste cathode carbon block of aluminum cell |
| CN104499000A (en) * | 2014-12-12 | 2015-04-08 | 平顶山华兴浮选工程技术服务有限公司 | Beneficiation treatment method for electrolytic aluminium carbon residues |
| CN204529994U (en) * | 2015-04-08 | 2015-08-05 | 沈阳银海机械设备制造有限公司 | The treatment unit of waste cathode carbon block in electrolysis of aluminum waste tank lining |
| CN106086938A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of ultrasonic assistant alkaline pressure of oxygen leaching reclaims the method for electrolyte in aluminium electroloysis waste lining |
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2016
- 2016-12-16 CN CN201611173533.5A patent/CN107055502A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020114748A1 (en) * | 1999-12-17 | 2002-08-22 | Vijaya Kasireddy | Recycling of spent pot linings |
| CN102146570A (en) * | 2011-02-26 | 2011-08-10 | 王建军 | Method for producing aluminum anode by using waste cathode carbon block of aluminum cell |
| CN104499000A (en) * | 2014-12-12 | 2015-04-08 | 平顶山华兴浮选工程技术服务有限公司 | Beneficiation treatment method for electrolytic aluminium carbon residues |
| CN204529994U (en) * | 2015-04-08 | 2015-08-05 | 沈阳银海机械设备制造有限公司 | The treatment unit of waste cathode carbon block in electrolysis of aluminum waste tank lining |
| CN106086938A (en) * | 2016-06-30 | 2016-11-09 | 中南大学 | A kind of ultrasonic assistant alkaline pressure of oxygen leaching reclaims the method for electrolyte in aluminium electroloysis waste lining |
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