CN104975219B - 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 53
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 51
- 239000011733 molybdenum Substances 0.000 title claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 46
- 239000001301 oxygen Substances 0.000 title claims abstract description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000012141 concentrate Substances 0.000 title claims abstract description 35
- 238000003723 Smelting Methods 0.000 title claims abstract description 29
- 229910001309 Ferromolybdenum Inorganic materials 0.000 title claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000010791 quenching Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims description 30
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 28
- 108010038629 Molybdoferredoxin Proteins 0.000 claims description 23
- HBELESVMOSDEOV-UHFFFAOYSA-N [Fe].[Mo] Chemical compound [Fe].[Mo] HBELESVMOSDEOV-UHFFFAOYSA-N 0.000 claims description 23
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 238000003556 assay Methods 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
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000005987 sulfurization reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000012858 packaging process Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- 238000007670 refining Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 230000003044 adaptive effect Effects 0.000 abstract 1
- 239000012467 final product Substances 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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 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
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-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
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000000171 quenching effect Effects 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
- 238000011410 subtraction method Methods 0.000 description 2
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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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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 based on effective oxygen in calcining molybdenum concentrate
Molybdenum-iron smelting process.
Background technology
Known, metallothermic processes is to go reduction little to oxygen affinity with the element (silicon, aluminum) big to oxygen affinity
Metal-oxide (molybdenum oxide), is common technique during molybdenum-iron produces with the method Smelting Ferromolybdenum technique, and process is divided into raw material accurate
The operations such as standby, proportioning calculating, batch mixing, loading smelting, calmness, slagging, lifting water quenching, broken finishing, chemical examination packaging.Smelting process
Chemical reaction releases substantial amounts of heat energy, enough alloy and slag is heated to necessary temperature and need not supply heat from extraneous, instead
Self-heating is answered to be smoothed out, thus isolating alloy and slag, therefore also referred to as perrin process.React the condition carrying out and depend on unit furnace charge
Chemical reaction heat effect, and then calculate depending on the oxygen balance in MaterialBalance Computation, material balance and Heat balance calculation
Whole metallothermic processes plays an important role.
Although traditional metallurgical calculating has rigorous material balance and Heat balance calculation, in its " oxygen " EQUILIBRIUM CALCULATION FOR PROCESS rank
Section, only assumes that the molybdenum in calcining molybdenum ore concentrate ore deposit is all existed with molybdenum trioxide form in the past, that is, 6+Valency molybdenum form exists, with chemistry
Molecular formula moo3Obtain its oxygen-containing coefficient of discharge: o3/ mo=16*3/96 is 0.5, with molybdenum mass percent in calcining molybdenum ore concentrate ore deposit with contain
The amassing of oxygen quotient 0.5 show that total oxygen carries out oxygen balance calculating, then determines excess coefficient 1-3%, and then calculates reducing agent use
Amount.Because the difference of roasting technique cause in calcining molybdenum concentrate contain the variable amount of molybdenum dioxide of 1-35% (4 valency), molybdenum sulfide and its
His molybdate, rather than " calcining molybdenum ore concentrate ore deposit is all existed with molybdenum trioxide form " assumed, the molybdenum of different valence state is to metal
The impact of " the oxygen balance calculating " of full-boiled process technique is extremely far-reaching, and the impact ignoring this factor is often made in actual production
Become reduction agent content and heat unstable, not only affect molybdenum-iron quality, also determine metal recovery rate, production cost, safety and environmental protection
Etc. production target, it plays a decisive role to the EQUILIBRIUM CALCULATION FOR PROCESS of total oxygen demand.
In the practical operation in its " oxygen " EQUILIBRIUM CALCULATION FOR PROCESS stage, also tend to rely on personal experience's correction result of technical staff
To organize actual production, because of the interference of various unpredictable factors, to lead to reducing agent except using personal experience as trade secret in addition to
Control unstable, and then lead to molybdenum-iron production economy technical specification wild effect frequently to occur, make molybdenum-iron Quality Down, production
Cost increase, is used for actual smelting with the method gained formulation data very inadvisable., also it is unfavorable for opening of molybdenum-iron metallurgical technology
Put formula development.
Content of the invention
In order to overcome the shortcomings of in background technology, the invention discloses a kind of based on effective oxygen in calcining molybdenum concentrate
Molybdenum-iron smelting process.
In order to realize described goal of the invention, the present invention adopts the following technical scheme that a kind of being based in calcining molybdenum concentrate effectively
The molybdenum-iron smelting process of oxygen content, the steps include:
(1) take batch calcining molybdenum concentrate classical assay method -- lead molybdate gravimetric method determines total molybdenum mass number；Use ammonia
The molten sedimentation method determine with solvable molybdenum trioxide (including solvable molybdate on a small quantity) mass number in batch calcining molybdenum concentrate, calculate
The mass percent of solvable molybdenum trioxide；
(2) sulfuration molybdenum content 1%, other insoluble molybdates 1%, total oxidation state molybdenum (molybdenum trioxide in predetermined calcining molybdenum concentrate
And molybdenum dioxide) content 98%, deduct solvable molybdenum trioxide mass percent with Subtraction method and draw its molybdenum dioxide percent mass
Than；Determine the thing phase composition mass percent of calcining molybdenum concentrate；
(3) following form calculates corresponding oxygen coefficient: moo respectively3 -: 48/96=0.5； moo2 -: 32/96=0.333；
(4) determine total oxygen coefficient of effective oxygen content in calcining molybdenum concentrate, equation below calculates:
∑ o=(moo3%*0.5+moo2%*0.333)*0.98
moo3% is moo3Mass percent；
moo2% is moo2Mass percent；
(5) actual according to needed for the effective oxygen content in calcining molybdenum concentrate calculates and excessive 10% determination Smelting Ferromolybdenum produces
Reducing agent consumption；Unclassified stores requirement determines according to a conventional method；
(6) proportioning, batch mixing, loading smelting, calmness, slagging, lifting are carried out according to the reducing agent consumption that step (5) calculates
Water quenching, broken finishing, chemical examination packaging process produce final products molybdenum-iron.
Due to employing technique scheme, the invention has the following beneficial effects: using this method energy scientific and efficient ground
Process different roasting techniques, different grades, the calcining molybdenum concentrate of different effective oxygens carries out molybdenum-iron smelting, adapts to wide, skill
Art skill requirement is low, the open development of suitable molybdenum-iron metallurgical technology；Especially it is to ensure that produced molybdenum-iron steady quality, reduce and smelt
Energy consumption and production cost, make molybdenum-iron smelting process environmental protection, safe efficient smooth carry out.
Specific embodiment
The explanation present invention that can be detailed by the following examples, the open purpose of the present invention is intended to protect model of the present invention
All technological improvements in enclosing.
Embodiment one
With 1000kg molybdenum oxide as unit of account.Molybdenum oxide: molybdenum 56%, wherein molybdenum trioxide content；Ferrosilicon: silicon amount 75%,
Aluminum 2%；Ferrum oxide: ferrum 65% molybdenum-iron product: molybdenum 61%
(1) take batch calcining molybdenum concentrate classical assay method -- lead molybdate gravimetric method determines total molybdenum mass number；Use ammonia
The molten sedimentation method determine with solvable molybdenum trioxide mass number in batch calcining molybdenum concentrate, calculate the quality hundred of solvable molybdenum trioxide
Divide and compare 82%；
(2) sulfuration molybdenum content 1%, other insoluble molybdates 1%, total oxidation state molybdenum content 98% in predetermined calcining molybdenum concentrate, use
Subtraction method deducts solvable molybdenum trioxide mass percent and draws its molybdenum dioxide mass percent moo2%；Determine roasting molybdenum essence
The thing phase composition mass percent of ore deposit is 0.98-0.82=16%；
1. oxygen coefficient: 0.5*0.82+(0.98-0.82) * 0.333=0.4632
Effective oxygen content=the 1000*56%*0.4632=259.392kg of molybdenum oxide
2. total oxygen demand: 259.392+280*0.9%*0.152(ferrum oxide) -55*0.99%*0.89(aluminum shot)=249.236kg
3. ferrosilicon amount needed for: 249.725/(1.143*0.75+0.889*0.02) * 1.1=313.2kg
4. other processes are omitted, and proportioning is as follows: molybdenum oxide 1000kg；Ferrosilicon 313 kg；Aluminum 55 kg；Ferrum oxide 280kg；
Steel cuttings 174 kg；Calcium oxide 98 kg.
5. furnace charge unit heat effect: 2210kj/kg
Comparative example
At identical conditions it is assumed that calcining molybdenum ore concentrate ore deposit is all existed with molybdenum trioxide form, that is, all 6+Valency molybdenum
Form exists, and its oxygen content is with chemical molecular formula moo3Obtain its oxygen-containing coefficient of discharge: o3/ mo=16*3/96 is 0.5, is being multiplied by molybdenum
Concentrate roasted ore amount containing molybdenum is obtained its total oxygen to calculate oxygen balance, then determines excess coefficient 1-3%, and then calculates reducing agent
Consumption.
1. oxygen coefficient: 0.5
Effective oxygen content=the 1000*56%*0.5=280kg of molybdenum oxide
2. total oxygen demand: 280+280*0.9*0.152(ferrum oxide) -55*0.99*0.89(aluminum shot)=269.844kg
3. ferrosilicon amount needed for: 269.844/(1.143*0.75+0.889*0.02) * 1.04=320kg
4. other processes are omitted, and proportioning is as follows: molybdenum oxide 1000 kg；Ferrosilicon 320 kg；Aluminum 55 kg；Ferrum oxide 280
kg；Steel cuttings 172 kg；Calcium oxide 98 kg.
5. furnace charge unit heat effect: 2221kj/kg actually 2198kj/kg
Because former method no considers the impact to calorific value for the content of molybdenum dioxide 14%, reduction reaction calorific value will be overestimated:
1000*56%*569kj=44609.6kj/1000kg molybdenum oxide, leaves hidden danger for extensive smelting.
If in calcining molybdenum concentrate, in esse molybdenum trioxide content fluctuation is bigger, then former method is inclined by result of calculation
Difference is bigger.
Accordingly, then the every stove of actual production puts into molybdenum oxide 4000kg meter, whole stove will have more 8*4=32kg ferrosilicon, for
The molybdenum-iron of " worrying about petty gain or loss " is smelted the consequence of bringing on a disaster property, single with regard to this calculate reducing agent cost increase 32*4 unit=128 yuan/
Stove, molybdenum-iron silicone content certainly will more than 1.5% the outer product of output level, also can lead to unit furnace charge calorific capacity mistake because reducing agent is superfluous
Height, and make reaction vigorous splash, produce potential safety hazard, smelting smoke dust leaks and induces environmental protection accident.
It can be seen that the determination of this oxygen coefficient more science.
Part not in the detailed description of the invention is prior art.
Claims (3)
1. a kind of molybdenum-iron smelting process based on effective oxygen in calcining molybdenum concentrate, is characterized in that: its preparation process is: (1)
Take batch calcining molybdenum concentrate classical assay method -- lead molybdate gravimetric method determines total molybdenum mass number；Determined with the molten sedimentation method of ammonia
With solvable molybdenum trioxide mass number in batch calcining molybdenum concentrate, calculate mass percent moo of solvable molybdenum trioxide3%；
(2) sulfuration molybdenum content 1%, other insoluble molybdates 1%, total oxidation state molybdenum content 98% in predetermined calcining molybdenum concentrate, use decrement
Method deducts solvable molybdenum trioxide mass percent and draws its molybdenum dioxide mass percent moo2%；Determine calcining molybdenum concentrate
Thing phase composition mass percent；
(3) following form calculates corresponding oxygen coefficient: moo respectively3 -: 48/96=0.5； moo2 -: 32/96=0.333；
(4) oxygen coefficient being drawn according to step (2) and step (3), determines the always oxygen-containing of effective oxygen content in calcining molybdenum concentrate
Coefficient；
(5) calculated according to total oxygen coefficient of the effective oxygen content in step (4) calcining molybdenum concentrate, determine that Smelting Ferromolybdenum produces institute
Need actual reducing agent consumption；Unclassified stores quantity determines according to a conventional method；
(6) proportioning, batch mixing, loading smelting, calmness, slagging, lifting water are carried out according to the reducing agent consumption that step (5) calculates
Quench, crush finishing, chemical examination packaging process produces final products molybdenum-iron.
2. the molybdenum-iron smelting process based on effective oxygen in calcining molybdenum concentrate as claimed in claim 1, is characterized in that: described
Total oxygen coefficient in step (4) is
∑ o=(moo3%*0.5+moo2%*0.333)
moo3% calculates the mass percent of molybdenum trioxide for step (1)；
moo2% calculates molybdenum dioxide mass percent for step (2).
3. the molybdenum-iron smelting process based on effective oxygen in calcining molybdenum concentrate as claimed in claim 1, is characterized in that: described
In step (5), calculated according to total oxygen coefficient of the effective oxygen content in step (4) calcining molybdenum concentrate, and excessive 10% determination smelting
The actual reducing agent consumption needed for producing of refining molybdenum-iron；Unclassified stores quantity determines according to a conventional method.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US1786393A (en) * | 1926-05-22 | 1930-12-23 | Schwarzkopf Paul | Method of producing ferromolybdenum and ferrotungsten |
| CN1008542B (en) * | 1987-01-19 | 1990-06-27 | 扬家杖子矿务局机电修配厂 | The method for preparing molybdenum-iron from molybdenum ore |
| CN101413880B (en) * | 2007-10-15 | 2010-12-08 | 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 |
| CN104152707B (en) * | 2014-08-28 | 2016-03-16 | 金堆城钼业股份有限公司 | A kind of ammonia leaching residue Smelting Ferromolybdenum reclaims the method for molybdenum |
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