CN104975219A - Ferro-molybdenum smelting method based on effective oxygen content in roasted molybdenum concentrate - Google Patents
Ferro-molybdenum smelting method based on effective oxygen content in roasted molybdenum concentrate Download PDFInfo
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 48
- 239000011733 molybdenum Substances 0.000 title claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 47
- 239000001301 oxygen Substances 0.000 title claims abstract description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000012141 concentrate Substances 0.000 title claims abstract description 36
- 238000003723 Smelting Methods 0.000 title claims abstract description 30
- 229910001309 Ferromolybdenum Inorganic materials 0.000 title claims abstract description 12
- 230000002829 reductive effect Effects 0.000 claims abstract description 12
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 32
- 108010038629 Molybdoferredoxin Proteins 0.000 claims description 22
- HBELESVMOSDEOV-UHFFFAOYSA-N [Fe].[Mo] Chemical compound [Fe].[Mo] HBELESVMOSDEOV-UHFFFAOYSA-N 0.000 claims description 22
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 16
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000003556 assay Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000007796 conventional method Methods 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 238000011410 subtraction method Methods 0.000 claims description 3
- 238000012858 packaging process Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract 2
- 230000003044 adaptive effect Effects 0.000 abstract 1
- 239000012467 final product Substances 0.000 abstract 1
- 238000010791 quenching Methods 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 9
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 8
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a ferro-molybdenum smelting method based on effective oxygen content in roasted molybdenum concentrate. Content of 4-valence and 6-valence salts as well as molybdate and molybdenum sulfide in a phase composition of the roasted molybdenum concentrate is analyzed and determined, corresponding oxygen coefficients are calculated respectively, and practical dose, required by production of smelting ferro-molybdenum, of a reducing agent is determined; and according to the calculated dose of the reducing agent, a final product ferro-molybdenum is produced by virtue of processes of purporting, mixing, charging and smelting, killing, slagging, lifting and water-quenching, crushing and finishing, testing and packaging. The method disclosed by the invention can be utilized to scientifically and efficiently treat the roasted molybdenum concentrate with different roasting processes, different grades and different effective oxygen content to carry out ferro-molybdenum smelting, is wide in adaptive range, low in technical experience requirement, suitable for open type development of a ferro-molybdenum smelting technology; and especially, the quality of the produced ferro-molybdenum is guaranteed to be stable, the smelting energy consumption and the production cost are reduced, so that the ferro-molybdenum smelting process is environmentally-friendly, safe and efficient.
Description
Technical field
The present invention relates to a kind of molybdenum-iron smelting process, especially relate to a kind of molybdenum-iron smelting process based on effective oxygen in calcining molybdenum concentrate.
Background technology
Known, metallothermics removes to reduce the metal oxide (molybdenum oxide) little to oxygen affinity with the element (silicon, aluminium) large to oxygen affinity, by the technique that this method Smelting Ferromolybdenum technique is common during molybdenum-iron is produced, process is divided into the operations such as raw material preparation, proportioning calculating, batch mixing, loading smelting, calmness, slagging, lifting shrend, broken finishing, chemical examination packaging.Smelting process chemical reaction releases a large amount of heat energy, enough alloy and slag is heated to required temperature and without the need to supplying heat from the external world, reaction self-heating carries out smoothly, thus isolates alloy and slag, therefore also claims perrin process.React the chemical reaction heat effect that the condition of carrying out depends on unit furnace charge, and then depend on that the oxygen balance in MaterialBalance Computation calculates, material balance and Heat balance calculation play an important role in whole metallothermics.
Although traditional metallurgy calculates rigorous material balance and Heat balance calculation, in its " oxygen " EQUILIBRIUM CALCULATION FOR PROCESS stage, the molybdenum in the past only in hypothesis calcining molybdenum ore concentrate ore deposit all exists with molybdic oxide form, namely 6
+valency molybdenum form exists, with chemical molecular formula MoO
3obtain its oxygen level coefficient: O
3/ Mo=16*3/96 is 0.5, show that total oxygen carries out oxygen balance calculating, then determines excess coefficient 1-3%, and then calculate reductive agent consumption with molybdenum mass percent in calcining molybdenum ore concentrate ore deposit and the amassing of oxygen coefficient 0.5.Difference because of sinter process causes the molybdenum dioxide (4 valency) containing 1-35% non-quantitative in calcining molybdenum concentrate, moly-sulfide and other molybdates, instead of " calcining molybdenum ore concentrate ore deposit all exists with molybdic oxide form " of hypothesis, the impact of molybdenum on " the oxygen balance calculating " of metal-thermic technique of different valence state is extremely far-reaching, the impact ignoring this factor often causes reductive agent content and heat instability in actual production, not only affect molybdenum-iron quality, also determine metal recovery rate, production cost, the productive capacitys such as safety and environmental protection, it plays a decisive role to the EQUILIBRIUM CALCULATION FOR PROCESS of total oxygen demand.
In the actually operating in its " oxygen " EQUILIBRIUM CALCULATION FOR PROCESS stage, also often rely on personal experience's correction result of technician to organize actual production, except using personal experience as except trade secret, because of the interference of various unpredictable factor, reductive agent is caused to control unstable, and then cause molybdenum-iron production economy technical indicator wild effect frequently to occur, make molybdenum-iron Quality Down, production cost increase, be used for actual smelting with this method gained formulation data very inadvisable., be also unfavorable for the open development of molybdenum-iron metallurgical technology.
Summary of the invention
in order to overcome the deficiency in background technology, the invention discloses a kind of molybdenum-iron smelting process based on effective oxygen in calcining molybdenum concentrate.
In order to realize described goal of the invention, the present invention adopts following technical scheme: a kind of molybdenum-iron smelting process based on effective oxygen in calcining molybdenum concentrate, the steps include:
(1) get batch calcining molybdenum concentrate classical assay method--lead molybdate weighting method determines total molybdenum total mass number; Determine, with molybdic oxide (comprising a small amount of solvable molybdate) total mass number solvable in batch calcining molybdenum concentrate, to calculate the mass percent of solvable molybdic oxide by the molten precipitator method of ammonia;
(2) moly-sulfide content 1%, other insoluble molybdates 1% in predetermined calcining molybdenum concentrate, total oxidation state molybdenum (molybdic oxide and molybdenum dioxide) content 98%, deducts solvable molybdic oxide mass percent with Subtraction method and draws its molybdenum dioxide mass percent; Determine the thing phase composite mass percent of calcining molybdenum concentrate;
(3) following form calculates corresponding oxygen coefficient respectively: MoO
3 -: 48/96=0.5; MoO
2 -: 32/96=0.333;
(4) total oxygen coefficient of effective oxygen level in calcining molybdenum concentrate is determined, following formulae discovery:
∑
o=（MoO
3%*0.5+MoO
2%*0.333)*0.98
MoO
3% is MoO
3mass percent;
MoO
2% is MoO
2mass percent;
(5) calculate according to the effective oxygen level in calcining molybdenum concentrate and excessive 10% determine that Smelting Ferromolybdenum produces required actual reductive agent consumption; Unclassified stores desired number is determined according to a conventional method;
(6) the reductive agent consumption calculated according to step (5) carry out proportioning, batch mixing, loading smelting, calmness, slagging, lifting shrend, broken finishing, chemical examination packaging process produce the finished product molybdenum-iron.
Owing to have employed technique scheme, the present invention has following beneficial effect: process different sinter process with utilizing present method energy scientific and efficient, different grade, the calcining molybdenum concentrate of different effective oxygen carries out molybdenum-iron smelting, adapt to wide, technical experience requires low, is applicable to the open development of molybdenum-iron metallurgical technology; Especially ensure that institute produces molybdenum-iron steady quality, reduction smelting energy consumption and production cost, make the environmental protection of molybdenum-iron smelting technology, safety, efficiently smooth and easyly to carry out.
Embodiment
By explanation the present invention that the following examples can be detailed, disclose object of the present invention and be intended to protect all technological improvements in the scope of the invention.
Embodiment one
With 1000KG molybdenum oxide for Units of Account.Molybdenum oxide: molybdenum 56%, wherein molybdic oxide content; Ferrosilicon: silicon amount 75%, aluminium 2%; Ferric oxide: iron 65% molybdenum-iron product: molybdenum 61%
(1) get batch calcining molybdenum concentrate classical assay method--lead molybdate weighting method determines total molybdenum total mass number; Determine, with molybdic oxide total mass number solvable in batch calcining molybdenum concentrate, to calculate the mass percent 82% of solvable molybdic oxide by the molten precipitator method of ammonia;
(2) moly-sulfide content 1%, other insoluble molybdates 1% in predetermined calcining molybdenum concentrate, total oxidation state molybdenum content 98%, deducts solvable molybdic oxide mass percent with Subtraction method and draws its molybdenum dioxide mass percent MoO
2%; The thing phase composite mass percent determining calcining molybdenum concentrate is 0.98-0.82=16%;
1. oxygen coefficient: 0.5*0.82+(0.98-0.82) * 0.333=0.4632
Effective oxygen level=the 1000*56%*0.4632=259.392KG of molybdenum oxide
2. total oxygen demand: 259.392+280*0.9%*0.152(ferric oxide)-55*0.99%*0.89(aluminum shot)=249.236KG
3. ferrosilicon amount: 249.725/(1.143*0.75+0.889*0.02 needed for) * 1.1=313.2KG
4. other processes are omitted, and proportioning is as follows: molybdenum oxide 1000KG; Ferrosilicon 313 KG; Aluminium 55 KG; Ferric oxide 280KG; Steel cuttings 174 KG; Calcium oxide 98 KG.
5. furnace charge unit heat effect: 2210KJ/KG
Comparative example
At identical conditions, supposing that calcining molybdenum ore concentrate ore deposit all exists with molybdic oxide form, is namely all 6
+valency molybdenum form exists, and its oxygen level is with chemical molecular formula MoO
3obtain its oxygen level coefficient: O
3/ Mo=16*3/96 is 0.5, obtains its total oxygen to calculate oxygen balance being multiplied by calcining molybdenum ore concentrate ore deposit containing molybdenum amount, then determines excess coefficient 1-3%, and then calculate reductive agent consumption.
1. oxygen coefficient: 0.5
Effective oxygen level=the 1000*56%*0.5=280KG of molybdenum oxide
2. total oxygen demand: 280+280*0.9*0.152(ferric oxide)-55*0.99*0.89(aluminum shot)=269.844KG
3. ferrosilicon amount: 269.844/(1.143*0.75+0.889*0.02 needed for) * 1.04=320KG
4. other processes are omitted, and proportioning is as follows: molybdenum oxide 1000 KG; Ferrosilicon 320 KG; Aluminium 55 KG; Ferric oxide 280 KG; Steel cuttings 172 KG; Calcium oxide 98 KG.
5. furnace charge unit heat effect: 2221KJ/KG is real is 2198KJ/KG
Because former method is without the impact of content on calorific value considering molybdenum dioxide 14%, reduction reaction calorific value will be over-evaluated: 1000*56%*569KJ=44609.6KJ/1000KG molybdenum oxide, leaves hidden danger for smelting on a large scale.
If in esse molybdic oxide content fluctuation is larger in calcining molybdenum concentrate, so former method is by larger for calculation result deviation.
Accordingly, so the every stove of actual production drops into molybdenum oxide 4000kg meter, whole stove will have more 8*4=32Kg ferrosilicon, molybdenum-iron for " worrying about petty gain or loss " is smelted the consequence of bringing on a disaster property, single calculates reductive agent cost increase 32*4 unit=128 yuan/stove at this point, and molybdenum-iron silicone content certainly will be greater than 1.5% and output level product outward, also unit furnace charge calorific value can be caused too high because reductive agent is superfluous, and make reaction vigorous splash, produce potential safety hazard, smelting smoke dust leaks and brings out environmental protection accident.
The determination comparatively science of this oxygen coefficient visible.
Part not in the detailed description of the invention is prior art.
Claims (3)
1. based on a molybdenum-iron smelting process for effective oxygen in calcining molybdenum concentrate, it is characterized in that: its preparation process is: (1) get batch calcining molybdenum concentrate classical assay method--lead molybdate weighting method determines total molybdenum total mass number; Determine, with molybdic oxide total mass number solvable in batch calcining molybdenum concentrate, to calculate the mass percent MoO of solvable molybdic oxide by the molten precipitator method of ammonia
3%;
(2) moly-sulfide content 1%, other insoluble molybdates 1% in predetermined calcining molybdenum concentrate, total oxidation state molybdenum content 98%, deducts solvable molybdic oxide mass percent with Subtraction method and draws its molybdenum dioxide mass percent MoO
2%; Determine the thing phase composite mass percent of calcining molybdenum concentrate;
(3) following form calculates corresponding oxygen coefficient respectively: MoO
3 -: 48/96=0.5; MoO
2 -: 32/96=0.333;
(4) according to the oxygen coefficient that step (2) and step (3) draw, total oxygen coefficient of effective oxygen level in calcining molybdenum concentrate is determined;
(5) calculate according to total oxygen coefficient of the effective oxygen level in step (4) calcining molybdenum concentrate, determine that Smelting Ferromolybdenum produces required actual reductive agent consumption; Unclassified stores quantity is determined according to a conventional method;
(6) the reductive agent consumption calculated according to step (5) carry out proportioning, batch mixing, loading smelting, calmness, slagging, lifting shrend, broken finishing, chemical examination packaging process produce the finished product molybdenum-iron.
2., as claimed in claim 1 based on the molybdenum-iron smelting process of effective oxygen in calcining molybdenum concentrate, it is characterized in that: the total oxygen coefficient in described step (4) is
∑
o=（MoO
3%*0.5+MoO
2%*0.333)*0.98
MoO
3% is the mass percent that step (1) calculates molybdic oxide;
MoO
2% is that step (2) calculates molybdenum dioxide mass percent.
3. as claimed in claim 1 based on the molybdenum-iron smelting process of effective oxygen in calcining molybdenum concentrate, it is characterized in that: in described step (5), total oxygen coefficient according to the effective oxygen level in step (4) calcining molybdenum concentrate calculates, and excessive 10% determines that Smelting Ferromolybdenum produces required actual reductive agent consumption; Unclassified stores quantity is determined according to a conventional method.
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|---|---|---|---|
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1786393A (en) * | 1926-05-22 | 1930-12-23 | Schwarzkopf Paul | Method of producing ferromolybdenum and ferrotungsten |
| CN87100348A (en) * | 1987-01-19 | 1987-07-29 | 杨家杖子矿务局机电修配厂 | The method for preparing molybdenum-iron from molybdenum ore |
| CN101413880A (en) * | 2007-10-15 | 2009-04-22 | 北京有色金属研究总院 | Fast analysis method of molybdenum in molybdenum concentrate |
| CN102251121A (en) * | 2011-07-06 | 2011-11-23 | 金堆城钼业股份有限公司 | Method for preparing industrial molybdenum trioxide by roasting ammonia leaching residue |
| CN104152707A (en) * | 2014-08-28 | 2014-11-19 | 金堆城钼业股份有限公司 | Method for smelting ferro-molybdenum from ammonia leaching residue to recover molybdenum |
-
2015
- 2015-05-29 CN CN201510285742.8A patent/CN104975219B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1786393A (en) * | 1926-05-22 | 1930-12-23 | Schwarzkopf Paul | Method of producing ferromolybdenum and ferrotungsten |
| CN87100348A (en) * | 1987-01-19 | 1987-07-29 | 杨家杖子矿务局机电修配厂 | The method for preparing molybdenum-iron from molybdenum ore |
| CN101413880A (en) * | 2007-10-15 | 2009-04-22 | 北京有色金属研究总院 | Fast analysis method of molybdenum in molybdenum concentrate |
| CN102251121A (en) * | 2011-07-06 | 2011-11-23 | 金堆城钼业股份有限公司 | Method for preparing industrial molybdenum trioxide by roasting ammonia leaching residue |
| CN104152707A (en) * | 2014-08-28 | 2014-11-19 | 金堆城钼业股份有限公司 | Method for smelting ferro-molybdenum from ammonia leaching residue to recover molybdenum |
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| Title |
|---|
| 罗晓丁等: "钼铁冶炼新的炉料计算方法", 《四川冶金》 * |
| 郑红: "简述炉外法冶炼钨铁及钼铁", 《有色冶矿》 * |
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Effective date of registration: 20211230 Address after: 471500 Miao Zi Zhen Shang He Cun, Luanchuan County, Luoyang City, Henan Province Patentee after: LUOYANG LUANCHUAN MOLYBDENUM GROUP SMELTING Co.,Ltd. Address before: 471500 Xindian Village, Xindian Town, high tech Development Zone, Luoyang City, Henan Province Patentee before: LUOYANG MOLYBDENUM GROUP METALLIC MATERIAL CO.,LTD. |
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Effective date of registration: 20240117 Address after: North of Yihe, Huameishan Road, Chengdong New District, Luanchuan County, Luoyang City, Henan Province, 471000 Patentee after: China Molybdenum Co.,Ltd. Address before: 471500 Miao Zi Zhen Shang He Cun, Luanchuan County, Luoyang City, Henan Province Patentee before: LUOYANG LUANCHUAN MOLYBDENUM GROUP SMELTING Co.,Ltd. |