CN102319634B - Process for recovering fuel from collophanite - Google Patents
Process for recovering fuel from collophanite Download PDFInfo
- Publication number
- CN102319634B CN102319634B CN 201110307314 CN201110307314A CN102319634B CN 102319634 B CN102319634 B CN 102319634B CN 201110307314 CN201110307314 CN 201110307314 CN 201110307314 A CN201110307314 A CN 201110307314A CN 102319634 B CN102319634 B CN 102319634B
- Authority
- CN
- China
- Prior art keywords
- flotation
- fuel
- ore
- carbon
- collophane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Solid Fuels And Fuel-Associated Substances (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses an ore dressing method for recovering fuel from collophanite. Flotation cells or flotation columns are serially connected. The process comprises the following steps of: making 20%-45% ore pulp from raw collophanite through crushing, grinding and grading, and fully mixing the ore pulp with a flotation agent in a mineralization tank to enter one flotation cell (column) for flotation, wherein the upper foam layer in the flotation cell (or flotation column) carbon-rich material (rough concentrates), and the bottom pulp material is carbon-poor tailings; uniformly mixing the rough concentrates with an ore dressing agent in another mineralization tank to enter another flotation device, wherein the bottom pulp material is carbon-poor tailings, and carbon in the upper foam layer is further enriched; repeating 3-5 times of flotation to obtain upper foam as fuel with high heat value. The invention provides one approach for comprehensively utilizing collophanite and has the advantages that the process is simple and stable and easy to automatic control, the heat value of the fuel is adjustable, and phosphorus in fuel cinder can be comprehensively recovered and the like.
Description
Technical field
The present invention relates to a kind of ore-dressing technique of phosphorus ore, especially relate to the technique that reclaims fuel in a kind of in the low-grade carbonaceous collophane.
Background technology
Small stream phosphate rock resource amount is washed in western part in the Hunan Province 500,000,000 tons, and proved reserves are 1.1 hundred million tons.This phosphorus ore belongs to carbon containing calcium siliceous phosphorite, and main valuable mineral is collophane, few apatite; Gangue mineral is take the carbon containing dolomite as main, and inferior is quartz, feldspar, carbon shale and hydromica etc., and calcite and pyrite are rare.Ore body is stratiform, and its top board and interlayer are in the majority with phosphorous dolomite, and phosphorous layer and phosphorous white clouds rock stratum be alternate with equal thickness not, form ribbon or lamellar structure; The phosphorus ore thing mostly is little---low carbonate fluorine apatite, be roe shape, false roe shape or gel-like structure, and wherein be wrapped with the thin loose gangue mineral of inequality.Contain higher carbonaceous in this phosphorus ore raw ore, reason is carbon containing or ore body country rock carbon containing in the ore body.What flotation was impacted mainly is the carbon that exists with graphite and flammable carbon (coal) form, this part carbon occupation rate in total carbon does not wait, difference is larger, but very obvious on the impact of flotation, the carbon of these particulates, because its surface nature is unique, in floatation process, a large amount of floating agent of carbon grain surface preferential adsorption changes the floatability of carbon granules self on the one hand, the difference that becomes is larger, consumes simultaneously a large amount of floating agents; On the other hand, carbon granules also very easily is adsorbed onto the mineral grain surface, affects medicament in the selective absorption on ore particle surface, thereby makes the floatability of various mineral become chaotic, the essence of Here it is usually said carbon contamination mineral surfaces.Secondly, owing to contain inevitably a certain amount of sludge (comprising that ore contains the sludge of mud and grinding process generation) in the ore, this part sludge is easy to carbon with particulate and mutually adsorbs or the peat agglomeration occurs, form peat matter, the part sludge is had in ore pulp and the similar behavior of fine-grained carbon, and becoming is difficult to disperse and suppresses and enter foam.In addition, also there is larger difference in the floatability of carbon itself, and when taking in advance decarburization, carbon can not more thoroughly remove, and causes carbon to be present in whole floatation process, all can be subject to the adverse effect of carbon in each stage grading, finally makes the phosphorus ore thing can not effective separation.Therefore, carbonaceous Collophanite flotation divided silicon, the calcareous front decarburization that needs.
Silico-calcium matter collophane ore dressing research has many decades historical in China, but the commercial Application of collophane ore dressing does not still have substantial breakthrough, does not abroad also have ripe experience in this respect.In recent decades western Hunan phosphorus ore was done a large amount of research, main technique has:
(1)Direct floatation process: raw ore contains phosphorus pentoxide 15.22%, objectionable impurities magnesia 4.08%, be milled down to the fineness of-200 orders 93.52% through ore grinding after, employing sodium carbonate is adjusting agent, S
808(sulfonation crude anthracene) is that inhibitor, spent pulping liquor are collecting agent, sorts through the one thick two direct flotation flow process of sweeping two essences, obtains containing phosphorus pentoxide 29.03%, magnesia 2.04%, the phosphorus concentrate of the rate of recovery 84.43%.Because medicament has larger toxicity, concentrate oxidation of impurities content of magnesium is higher, does not use in this explained hereafter.
(2)Just-reverse floatation process: raw ore phosphorus pentoxide grade 17.97%, by just-to obtain concentrate grade be 29.59% to reverse flotation, overall recovery 63.72%.Concentrate yield 36.40%, ratio of concentration 2.58.Because cost is higher, do not use in this explained hereafter.
(3)Heavymedia separation: wash the phosphorus concentrate of small stream phosphorus ore after heavymedia separation, contain phosphorus pentoxide 25.43%, magnesia 2.95%, phosphorus yield are 70.73%.Concentrate does not reach acid system phosphoric acid to the requirement of raw material.
Summary of the invention
The object of the present invention is to provide the ore-dressing technique that reclaims fuel in a kind of in the low-grade carbonaceous collophane.
The present invention is achieved by the following technical solutions, and it may further comprise the steps: (1) with ore reduction, wet-milling to-200 order content are 92～97% fineness; (2) floatation enrichment carbon adopts flotation cell or flotation column to be connected in series.The phosphorus ore raw ore is made 20%～45% ore pulp after fragmentation, ore grinding and classification, in the mineralising groove with behind the abundant mixing of floating agent, enter flotation in the flotation cell (or flotation column), flotation cell (or flotation column) upper foam layer is for needing the again rich carbon rough concentrate of choosing, and the slurry of bottom is poor carbon mine tailing.Rough concentrate is entered another flotation cell (or flotation column) in another mineralising groove with after selecting the medicament mixing, the slurry of bottom is poor carbon chats, and rough concentrate needs further enrichment.Carry out 3～5 upper foam layer after selected and be the higher fuel of phosphorus content.Flotation is generally carried out in neutral medium, and the main medicament of employing is kerosene, diesel oil, fuel oil, heavy oil, transformer wet goods, and consumption is 0.25～0.75Kg/t, flotation time 5～30 minutes.Dry basic high calorific power (Qgr, v, the d) 5～20MJ/Kg of gained fuel.The invention provides a kind of approach of collophane comprehensive utilization, have the technique simple and stable, easily automatically control.The recyclable phosphate of tailings after the fuel combustion has reduced the loss of phosphorus.(3) phosphate enrichment, the ore pulp after the floatation decarburization (or mix with tailings after the fuel combustion that the technical program reclaims) enters phosphate rock floating enrichment flow process.Phosphate rock floating enrichment flow process mainly comprise phosphate just-reverse floatation process, direct flotation technique, reverse floatation process etc.Here use phosphate just-reverse floatation process: the phosphate direct flotation carries out in alkaline medium, adjusting agent is selected from a kind of in sodium carbonate, waterglass, NaOH, the polyphosphate or their mixture, carbonate inhibitor (such as FY-8), collecting agent are selected from a kind of in fatty acid, oxidized paraffin wax soap, tall oil, the soap class or derivatives thereof or their mixture (such as FZ-6).Through one roughing, the flotation operation of once purging selection is discharged the silicate mine tailing, and floating agent dosage and time are: roughly select sodium carbonate 2～8Kg/t, waterglass 0～8Kg/t, FY-8 consumption 0.2～0.7 Kg/t, FZ-6 consumption 0.3～0.9 Kg/t, flotation time 3～20 minutes; Scan FZ-6 consumption 0.2～0.4 Kg/t, flotation time 3～15 minutes; The froth pulp of direct flotation enters the carbonate reverse flotation work, and reverse flotation carries out in the weak acidic medium of pH4～6, and floating agent is generally take nitration mixture as inhibitor, take fatty acid (such as FZ-6) as collecting agent.Through one roughing, once counter scanning, once anti-selected operation, discharge carbonate tailings, floating agent dosage and time are: roughly select nitration mixture (being generally the mixture of phosphoric acid and sulfuric acid) consumption 3～10Kg/t raw ore, FZ-6 consumption 0.5～3Kg/t raw ore, flotation time 5～25 minutes; Scan FZ-6 consumption 0.2～4Kg/t raw ore, flotation time 2～15 minutes; Selected nitration mixture consumption 0.5-3 Kg/t raw ore, flotation time 5～15 minutes; It is final products phosphorus concentrate that reverse flotation is scanned the interior product of post-job groove, can reach phosphoric acid by wet process concentrate grade III Standard.
The present invention is used for western Hunan carbonaceous mid-low grade collophanite ore, can comprehensively reclaims the higher fuel of calorific value, gained fuel can be used for baking bricks, burnt lime or other side, and can be from slag recovery section phosphorus.
It is low that the present invention has overcome calcining-digestion-spiral mineral concentrate rate of recovery, the shortcoming that energy consumption is high, the phosphorus pentoxide rate of recovery than simple just-reverse flotation improves 1～5%.
The present invention can Effective Raise the recovery rate in ore-dressing of western Hunan carbonaceous collophane, make western Hunan carbonaceous collophane and other similar rock phosphate in powder can obtain the effective exploitation utilization, for the sustainable development of China's sulphur dioxide of phosphor chemical industry plays a significant role.
The specific embodiment
The present invention will be further described below in conjunction with test example, but they are not the restriction to protection domain of the present invention.
Test example 1
(1) western Hunan mining area exploitation ore out, the phosphorus pentoxide grade is 16.53%, objectionable impurities magnesia 7.03%, organic carbon content 5.22%.Passing through fragmentation-ore grinding, is 96.1% fineness with ore wet-milling to-200 order content;
(2) floatation enrichment carbon carries out in the medium of normal temperature alkali-free, adopts the one roughing recleaning, and cleaner tailings returns with the raw ore ore pulp and merges, and selected concentrate is fuel, and the dry basic high calorific power of fuel reaches 7.10MJ/Kg, and productive rate is 8.6%.Roughly select and add collecting agent 0.55Kg/t raw ore, flotation time 3～10 minutes.Selected adding medicine 0 ~ 0.25Kg/t raw ore, flotation time 10～20 minutes.Fuel residues aquation, classification enter the phosphate flotation flowsheet after taking off removing calcium and magnesium hydroxide;
(3) product carries out the phosphate direct flotation in the phosphate direct flotation, the groove after the floatation decarburization, carries out in the alkaline medium of phosphate direct flotation about 18 degrees centigrade, and through one roughing, the flotation operation of once purging selection is discharged the silicate mine tailing.Roughly select sodium carbonate amount 8Kg/t raw ore, FY-8 inhibitor 0.5 Kg/t raw ore, FZ-6 collecting agent 0.6Kg/t, flotation time 5～15 minutes; Scan sodium carbonate amount 3Kg/t raw ore, FY-8 inhibitor 0.1 Kg/t raw ore, FZ-6 collecting agent 0.3Kg/t, flotation time 5～12 minutes;
(4) carbonate reverse flotation, the direct flotation froth pulp enters the carbonate reverse flotation work, reverse flotation carries out in the weak acidic medium of pH=4～6, through one roughing, once purging selection, primary cleaning operation, discharge carbonate tailings and thin mud, floating agent dosage and time are: roughly select nitration mixture consumption 7.5Kg/t, the FZ-6 consumption is zero, flotation time 5～15 minutes; Nitration mixture is scanned nitration mixture consumption 1.0Kg/t, and the FZ-6 consumption is 0.6Kg/t, flotation time 3～12 minutes; After reverse flotation is scanned operation, can obtain phosphorus pentoxide content greater than 30%, the objectionable impurities content of magnesia is less than 1.5% qualified concentrate containing.
Test example 2
(1) western Hunan mining area exploitation ore out, the phosphorus pentoxide grade is 16.53%, objectionable impurities magnesia 7.03%, organic carbon content 5.22%.Passing through fragmentation-ore grinding, is 93.7% fineness with ore wet-milling to-200 order content;
(2) the floatation decarburization is carried out in the medium of normal temperature alkali-free, adopts the one roughing triple cleaning, and cleaner tailings and raw ore ore pulp merge, and selected concentrate is fuel, and the dry basic high calorific power of fuel reaches 10.59 MJ/Kg, and productive rate is 5.8%; Can select the fuel residues aquation, classification enters the phosphate flotation flowsheet after taking off removing calcium and magnesium hydroxide.
Ore pulp after the decarburization is roughly selected and is added collecting agent 0.55Kg/t raw ore, flotation time 3～10 minutes.Selected adding medicine 0 ~ 0.25Kg/t raw ore, flotation time 10～20 minutes.
Test example 3
(1) western Hunan mining area exploitation ore out, the phosphorus pentoxide grade is 15.83%, objectionable impurities magnesia 5.01%, organic carbon content 7.12%.Passing through fragmentation-ore grinding, is 94.8% fineness with ore wet-milling to-200 order content;
(2) the floatation decarburization is carried out in the medium of normal temperature alkali-free, adopts the one roughing triple cleaning, and cleaner tailings and raw ore ore pulp merge, and selected concentrate is fuel, and the dry basic high calorific power of fuel reaches 10.59 MJ/Kg, and productive rate is 6.9%; Can select the fuel residues aquation, classification enters the phosphate flotation flowsheet after taking off removing calcium and magnesium hydroxide; Ore pulp after the decarburization adopts floatation process to produce the phosphorus concentrate.
Claims (7)
1. reclaim the beneficiation method of fuel in the collophane, it is characterized in that the method may further comprise the steps:
(1) floatation enrichment carbon carries out in the normal temperature neutral medium, and selective flotation groove or flotation column are flotation unit;
(2) the collophane raw ore is through broken, ore grinding and classification, mog be-200 orders greater than 90%, make the mineral composition monomer dissociation, controlling pulp density is 20%～45%;
(3) ore pulp of step (2) is introduced in the pulp tank, and the conventional floating agent of adding fully mixes with ore pulp;
(4) gains of step (3) are introduced in the described flotation unit of step (1), carried out flotation operation;
(5) ore pulp of flotation cell or flotation column bottom is poor carbon mine tailing, and poor carbon mine tailing is sent to follow-up phosphate sorting flow process;
(6) froth bed on flotation cell or flotation column top is rough concentrate, rough concentrate is introduced in another pulp tank, and the conventional floating agent of adding fully mixes with ore pulp;
(7) step (6) gains are introduced in the described flotation unit, carried out carbonaceous enrichment flotation operation;
(8) froth bed on flotation cell or flotation column top is rough concentrate, and the ore pulp of flotation cell or flotation column bottom is poor carbon mine tailing, and poor carbon mine tailing is sent to the phosphate flotation flowsheet;
(9) rough concentrate of step (8) is introduced in another pulp tank, and the conventional floating agent of adding fully mixes with ore pulp;
(10) repeat (7), (8), (9) step 2 time to 5 times, the froth bed on flotation cell or flotation column top is concentrate, and concentrate obtains required finished product fuel through concentrated, filtering means dehydration.
2. reclaim the beneficiation method of fuel in the collophane according to claim 1, it is characterized in that consisting of of collophane ore: phosphorus pentoxide grade 15～30%, content of magnesia 2～10%, organic carbon content 2%～10%, carbonate content do not wait.
3. reclaim the beneficiation method of fuel in the collophane according to claim 1, it is characterized in that, the butt fuel content of combustible carbon 15%～55% that obtains in the fuel that described method reclaims, butt fuel productive rate 2%～20%, the dry basic high calorific power of fuel reaches 5～20MJ/Kg, and fuel productive rate and calorific value are decided on composition of ores content and butt fuel content of combustible carbon.
4. reclaim according to claim 1 the beneficiation method of fuel in the described collophane, it is characterized in that the capital equipment that adopts is flotation cell or flotation column, the aeration quantity parameter can be regulated as required in the floatation process.
5. the described beneficiation method that reclaims fuel from collophane according to claim 1 is characterized in that the main medicament kind that adopts is identical with the medicament of common floatation process, i.e. kerosene, diesel oil, heavy oil, transformer oil.
6. the beneficiation method that from collophane, reclaims fuel according to claim 1, it is characterized in that, described floating agent dosage and time are: flotation collector consumption 0.10～0.85Kg/t raw ore, assistant medicament consumption 0.00～0.65Kg/t raw ore, single flotation time 3～30 minutes.
7. reclaim the beneficiation method of fuel in the collophane according to claim 1, it is characterized in that, contain more phosphorus in the residue after the fuel combustion of reclaiming in the described collophane, can be used for the phosphate fertilizer raw material or with resolution method, the recovery of floatation process synthesis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110307314 CN102319634B (en) | 2011-10-12 | 2011-10-12 | Process for recovering fuel from collophanite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110307314 CN102319634B (en) | 2011-10-12 | 2011-10-12 | Process for recovering fuel from collophanite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102319634A CN102319634A (en) | 2012-01-18 |
| CN102319634B true CN102319634B (en) | 2013-04-10 |
Family
ID=45447539
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110307314 Expired - Fee Related CN102319634B (en) | 2011-10-12 | 2011-10-12 | Process for recovering fuel from collophanite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102319634B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105233991B (en) * | 2015-09-17 | 2018-02-02 | 中国铝业股份有限公司 | A kind of method that inverse floatation of bauxite synchronized desulfuring takes off organic matter |
| CN108927294A (en) * | 2017-05-24 | 2018-12-04 | 中蓝连海设计研究院 | A kind of method for floating of silicon calcium collophanite |
| CN112808463B (en) * | 2020-12-30 | 2022-06-21 | 中南大学 | Medicament and method for flotation separation of iron-titanium ore and iron-containing gangue |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1086438A (en) * | 1965-12-09 | 1967-10-11 | Zuplatec A G Ges Fuer Tech Pla | Concentration of phosphate ores |
| CN1322934C (en) * | 2005-07-30 | 2007-06-27 | 中蓝连海设计研究院 | Collophanite direct flotation and reverse flotation technique |
| CN101099946A (en) * | 2007-07-13 | 2008-01-09 | 云南省化工研究院 | Collophanite floatation method |
| CN101905190B (en) * | 2010-07-05 | 2012-11-28 | 北京矿冶研究总院 | Collophanite beneficiation method |
-
2011
- 2011-10-12 CN CN 201110307314 patent/CN102319634B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN102319634A (en) | 2012-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1322934C (en) | Collophanite direct flotation and reverse flotation technique | |
| CN104689913B (en) | A kind of method that polycrystalline series troilite mixing is reclaimed | |
| CN101099946A (en) | Collophanite floatation method | |
| CN102921551A (en) | Fluorite mineral flotation method | |
| CN105032598A (en) | Method for floatation of preconcentration vanadium from high-calcium mica type vanadium-bearing stone coal | |
| CN101759165A (en) | Method for recovering P2O5 in phosphorus ore dressing mill tailings | |
| CN105750089B (en) | A kind of magnesia collophane method for separating | |
| CN105597939A (en) | Process for mineral processing of low-grade silicon calcium collophanite | |
| CN100519783C (en) | Technique for comprehensive utilization clean production of phosphorus block ore and extracting rare earth form the phosphorus block ore | |
| CN105921258A (en) | Method for impurity removal and whitening of potassium feldspar | |
| CN101602031A (en) | A kind of combined capturing and collecting agent of apatite | |
| CN115418498B (en) | Treatment method of carbonate lithium clay | |
| CN102319634B (en) | Process for recovering fuel from collophanite | |
| CN101264466B (en) | High phosphorus and sulphur siderite full flotation mineral separation method | |
| CN108580050A (en) | A kind of neutral pH conditions flotation potassium feldspar method | |
| CN104891855A (en) | A method of extracting rare earth sulfate from coal gangue and applying the rare earth sulfate as a concrete additive | |
| CN111330744A (en) | Flotation method and pretreatment method for phosphate rock containing calcite | |
| CN111644269B (en) | Method for comprehensively utilizing electrolytic manganese slag resources | |
| CN107381525A (en) | Utilize the technique and device of mid-low grade collophanite ore production industrial monoammonium phosphate coproduction high-quality MAP | |
| CN106495623B (en) | A method of steam-pressing brisk is prepared using molybdic tailing | |
| CN106179731B (en) | The method of sesquichloride and magnesium in the single reverse flotation coupling abjection phosphorus ore of high-gradient magnetic separation | |
| CN107335531A (en) | A kind of method of separation by shaking table phosphorus ore | |
| CN104801425B (en) | A kind of phosphorus ore is classified many grade floatation process of dosing in batches | |
| CN105013617A (en) | Collophanite dressing technology | |
| CN100369850C (en) | Comprehensive utilization method for coal gangue and phosphogypsum |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130410 Termination date: 20151012 |
|
| EXPY | Termination of patent right or utility model |