CN105907992B - A kind of method that pressure oxidation detaches molybdenum, copper and rhenium in Low Grade Molybdenum Concentrates - Google Patents
A kind of method that pressure oxidation detaches molybdenum, copper and rhenium in Low Grade Molybdenum Concentrates Download PDFInfo
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Abstract
The present invention provides a kind of methods that pressure oxidation detaches molybdenum, copper and rhenium in Low Grade Molybdenum Concentrates, include the following steps：One, it is sieved after being ground to Low Grade Molybdenum Concentrates, then plus water is configured to ore pulp；Two, pressure oxidation in autoclave pressure is added in ore pulp, nitrogenous compound and sulfuric acid to react, obtains slurry；Three, vacuum filter obtains filter cake and the first filtrate；Four, filter cake is washed, obtains industrial molybdenum oxide；Washing lotion after washing is merged with the first filtrate, then iron powder, iron filings or iron wire are added in mixed liquor, it stands, filter after stirring evenly, obtain filter residue and the second filtrate, by filter residue melting copper, using in the second filtrate of ion exchange resin pair molybdenum and rhenium adsorb, then substep desorption recycling molybdenum and rhenium.A molybdenum recovery of the invention is up to 90%, and molybdenum oxygenation efficiency is high, and required pressure is small, and temperature is low, and the reaction time is short, and metal synthetical recovery effect is good.In short, present invention process reasonable design, using effect is good, and economic value is high.
Description
Technical field
The invention belongs to rare precious metals recovery technology fields, and in particular to a kind of pressure oxidation separation Low Grade Molybdenum Concentrates
The method of middle molybdenum, copper and rhenium.
Background technology
Molybdenum plays an important role to the sustainable development of human society.Molybdenum makes an addition to steel or cast iron, can improve its intensity, hard
Degree and toughness；Applied to stainless steel or high temperature alloy, its anticorrosive and high-temperature behavior can be improved, be largely used to automobile, shipbuilding, build
It builds, dig up mine, oil gas and energy industry.In addition, molybdenum chemical industry also there are many application, for produce catalyst, lubricant and
Pigment.
The oxide of molybdenum is the main source of molybdenum application.It is made by the molybdenum disulfide that molybdenite flotation obtains by aoxidizing.
Many research activities are dedicated to the improvement of the oxidation technology of molybdenum.
Currently, the technique for producing industrial molybdenum oxide by molybdenum concntrate both at home and abroad is mainly pyrogenic process roasting, i.e., by molybdenum concntrate anti-
It penetrates in stove, multiple hearth furnace or rotary kiln in 600 DEG C or so oxidizing roastings, molybdenite desulfurization is made to be oxidized into industrial molybdenum oxide.Roasting
There are following technological deficiencies for technique：The oxidation of molybdenum is incomplete, also includes a large amount of MoO in molybdenum oxide2, cause then to produce molybdenum
Molybdenum is largely lost when sour ammonium；Roasting process generates largely flue gas and flue dust containing low-concentration sulfur dioxide, needs additional high
Flue gas and flue dust collecting and desulfurizer recycling molybdenum and purification gas；It is not suitable for the high molybdenum concntrate of copper oxide, iron content, roasts
The thick molybdenum oxide purity that such molybdenum concntrate obtains is low, it is also necessary to carry out refining and edulcoration；It is not suitable for aoxidizing rhenium-containing molybdenum concntrate.If molybdenum
Contain dissipated metal rhenium in concentrate, during oxidizing roasting, rhenium is scattered in flue gas, flue dust and molybdenum calcining, it is difficult in high yield
Rhenium is carried, the rhenium wasting of resources is caused.
Compared with traditional pyrogenic process roasting technique, pressure oxidation technique can be not only used for producing industrial molybdenum oxide from molybdenum concntrate,
It can be used for, by Low Grade Molybdenum Concentrates or molybdenum intermediate products production ammonium molybdate or pure molybdenum trioxide, solving pyrogenic process roasting to a certain degree again
The defect of firing technique.
Patent document below is related to the research in relation to molybdenum concntrate pressure oxidation technique.
1962, a Japan Patent reported Sada, the pressure oxidation reaction for the molybdenite that Koji is done, which exists
In one embodiment, in the case where the oxygen of 200 DEG C and 200 atmospheric pressure acts on, extracts and contained Mo55.5%, S36.4%, Cu4.4%
Molybdenum concntrate.
US4512958 improves above-mentioned technology.The molybdenum concntrate that particle size is increased to 90um by the technique adds water slurry, so
Pressure oxidation reaction is carried out at raised temperature and partial pressure of oxygen afterwards, at 230~245 DEG C, partial pressure of oxygen controls for system temperature control
In 0.1~0.5KPa ranges.After reaction, filters the autoclaving liquid containing sulfuric acid and form first-time filtrate, this filtrate is through lime or carbonic acid
In calcium and formed gypsum.The emphasis of the technology is that serum density is maintained at 100~150g/L by circulation secondary filtrate.
The technology of WO2008/063986 Oxidation under pressurized oxygen molybdenum concntrates include deoil, leach, Oxidation under pressurized oxygen, separation of solid and liquid, solvent
Extraction or ion exchange, elution and ion-exchange step.Pressure oxidation reaction 225 DEG C of temperature, the pressure of 3MPa and
It is carried out under the partial pressure of oxygen of 0.7MPa.
After aoxidizing molybdenum concntrate using pressure oxidation technique, the sulfide minerals impurity such as copper, iron, zinc for containing in molybdenum concntrate enters
Solution, molybdenum are oxidized to soluble and insoluble molybdic acid.Insoluble molybdic acid also contains silicate and alumino-silicate gangue mineral, can be with
Extracted through alkali pure, then acid is heavy or is concentrated by evaporation ammonium molybdate processed, can also wash, dries industrial molybdenum oxide is made；Molybdenum acid solution can
To produce ammonium molybdate through extraction or ion exchange.
But there is also many deficiencies for existing molybdenum concntrate pressure oxidation technique, such as：Reaction pressure is big, and reaction temperature is high, instead
It is long etc. between seasonable.
Invention content
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of pressure oxidation point
Method from molybdenum, rhenium and copper in Low Grade Molybdenum Concentrates.Molybdenum recovery of this method can be of about 90%, and molybdenum oxygenation efficiency is high；It is required
Pressure is small, and temperature is low, and the reaction time is short；Metal synthetical recovery effect is good.In short, this method technological design is reasonable, using effect
Good, economic value is high.
In order to solve the above technical problems, the technical solution adopted by the present invention is：A kind of low-grade molybdenum essence of pressure oxidation separation
The method of molybdenum, copper and rhenium in mine, which is characterized in that this approach includes the following steps：
Step 1: being ground to Low Grade Molybdenum Concentrates, 200 mesh sieve is then crossed, molybdenum concntrate powder is obtained, later will
Molybdenum concntrate powder is added in deionized water, obtains ore pulp after mixing；
Step 2: ore pulp described in step 1, nitrogenous compound and sulfuric acid are added in autoclave pressure, then into reaction kettle
It is passed through oxygen, is 150 DEG C~180 DEG C in temperature, pressure oxidation reaction 1h, obtains under conditions of pressure is 1.0MPa~1.5MPa
Slurry；
Step 3: carrying out vacuum filter processing to slurry described in step 2, filter cake and the first filtrate are obtained；
Step 4: being washed to filter cake described in step 3 using deionized water, industrial molybdenum oxide is obtained after dry；It will
Washing lotion after washing merges with first filtrate, obtains mixed liquor, and then iron powder, iron filings or iron wire are added in mixed liquor,
It is filtered after stirring evenly, obtains filter residue and the second filtrate, later by filter residue melting copper, filtered using ion exchange resin pair second
Molybdenum and rhenium in liquid are adsorbed, finally using the method recycling molybdenum and rhenium of substep desorption.
The method of molybdenum, copper and rhenium in a kind of above-mentioned pressure oxidation separation Low Grade Molybdenum Concentrates, which is characterized in that step 1
Described in Low Grade Molybdenum Concentrates the mass percentage of molybdenum be 42%~53%, the mass percentage of copper is 0.5%~
5%, the mass percentage of rhenium is 0.1%~0.8%.
The method of molybdenum, copper and rhenium in a kind of above-mentioned pressure oxidation separation Low Grade Molybdenum Concentrates, which is characterized in that step 1
Described in the addition of deionized water be 5~20 times of molybdenum concntrate powder quality.
The method of molybdenum, copper and rhenium in a kind of above-mentioned pressure oxidation separation Low Grade Molybdenum Concentrates, which is characterized in that step 2
Described in nitrogenous compound be any one or two kinds in nitric acid, potassium nitrate, sodium nitrate, potassium nitrite and sodium nitrite with
On.
The method of molybdenum, copper and rhenium in a kind of above-mentioned pressure oxidation separation Low Grade Molybdenum Concentrates, which is characterized in that step 2
Described in the addition of nitrogenous compound be the 5%~40% of molybdenum concntrate powder quality, the addition of the sulfuric acid is molybdenum concntrate
The 0.5%~2% of powder quality.
The method of molybdenum, copper and rhenium in a kind of above-mentioned pressure oxidation separation Low Grade Molybdenum Concentrates, which is characterized in that step 4
Described in the molal quantity of iron powder, iron filings and iron wire be 1.05~1.15 times of copper molal quantity in Low Grade Molybdenum Concentrates.
The present invention is based on sulfide minerals below to meet the theoretical foundation that sulfuric acid and nitrogenous compound react, nitrogenous chemical combination
Object is by taking nitric acid as an example：
3MeS+2HNO3+3H2SO4→3MeSO4+3S+2NO+4H2O
NaNO2+H+→HNO2+Na+
HNO2+H+→NO++H2O
2MeS+4NO+→2Me+2+2S+4NO
It can further be oxidized to sulfuric acid in higher temperature sulphur：
2H2O+2S+3O2→2H2SO4
Under conditions of nitrogenous compound assisted oxidation, the metallic element in sulfide mineral enters solution, and sulphur is oxidized to list
Matter is further oxidized to sulfuric acid.Wherein：
NO regenerates NO+, make reaction continue to carry out, thus, the present invention can realize molybdenum at relatively low temperatures and pressures
The oxidation of concentrate especially rhenium-containing molybdenum concntrate.
The present invention has the advantage that compared with prior art：
1, the present invention enhances molybdenum concntrate oxidation reaction, reduces reaction by the addition of nitrogenous compound reaction promoter
Temperature and reaction pressure, shorten the reaction time.
2, present invention process reasonable design.After oxidation, about 90% molybdenum is oxidized to solid-state molybdic acid in molybdenum concntrate, can dry
Directly form product.All enrichment enters solution to other valuable metals, is conducive to recycling extraction.
3, using effect of the present invention is good.The oxygenation efficiency of molybdenum is up to 99% or more.The rate of recovery of molybdenum can theoretically reach
100%.
4, smoke dust of the present invention, exhaust emission will not cause damages to external environment.Sulphur in molybdenum concntrate is oxidized to sulphur
Acid, no SO2、SO3It generates, exhuast gas desulfurization problem is not present.
With reference to embodiment, invention is further described in detail.
Specific implementation mode
Embodiment 1
The Low Grade Molybdenum Concentrates that the present embodiment need to be handled contain the various composition of following weight percent：Mo 52.37%,
Re 0.16%, Cu 1.5%, Ca 0.08%, P 0.11%, S 31.58%, Fe 2.73%, SiO210.83%.This implementation
The method of molybdenum, copper and rhenium includes the following steps in example pressure oxidation separation Low Grade Molybdenum Concentrates：
Step 1: being ground to Low Grade Molybdenum Concentrates, 200 mesh sieve is then crossed, molybdenum concntrate powder is obtained, later will
50g molybdenum concntrate powder is added in deionized water, and the addition of the deionized water is 10 times of molybdenum concntrate powder quality, and mixing is equal
Ore pulp is obtained after even；
Step 2: ore pulp described in step 1, nitrogenous compound and sulfuric acid are added in autoclave pressure, then into reaction kettle
It is passed through oxygen, is 150 DEG C in temperature, pressure reacts 1h under conditions of being 1.5MPa, obtains slurry；The nitrogenous compound is nitre
The addition of acid, the nitrogenous compound is 10g (being the 20% of molybdenum concntrate powder quality), and the addition of the sulfuric acid is molybdenum
The 2% of concentrate powder quality；
Step 3: carrying out vacuum filter processing to slurry described in step 2, filter cake and the first filtrate are obtained；
Step 4: being washed to filter cake described in step 3 using deionized water, industrial molybdenum oxide is obtained after dry；It will
Washing lotion after washing merges with first filtrate, obtains mixed liquor, and then iron powder, iron filings or iron wire are added in mixed liquor,
The molal quantity of the iron powder, iron filings and iron wire is 1.1 times of copper molal quantity in Low Grade Molybdenum Concentrates, is filtered after stirring evenly,
Obtain filter residue and the second filtrate, later by filter residue melting copper, using in the second filtrate of ion exchange resin pair molybdenum and rhenium into
Row absorption, finally using the method recycling molybdenum and rhenium of substep desorption.
It is calculated through weighing, the weight that the present embodiment obtains industrial molybdenum oxide is 37.3g, and molybdenum oxygenation efficiency is 99%.
Embodiment 2
The present embodiment the difference is that only with embodiment 1：Nitric acid, remaining technical process and ginseng are replaced with 5g sodium nitrate
Said conditions are same as Example 1.
It is calculated through weighing, the weight that the present embodiment obtains industrial molybdenum oxide is 40.8g, and molybdenum oxygenation efficiency is 98.1%.
Embodiment 3
The present embodiment the difference is that only with embodiment 1：With 2.5g potassium nitrate replace nitric acid, remaining technical process and
Parameter Conditions are same as Example 1.
It is calculated through weighing, the weight that the present embodiment obtains industrial molybdenum oxide is 42.1g, and molybdenum oxygenation efficiency is 96.7%.
Embodiment 4
The present embodiment the difference is that only with embodiment 1：Nitric acid, remaining technical process are replaced with 15g potassium nitrites
And Parameter Conditions are same as Example 1.
It is calculated through weighing, the weight that the present embodiment obtains industrial molybdenum oxide is 40.5g, and molybdenum oxygenation efficiency is 98.5%.
Embodiment 5
The present embodiment the difference is that only with embodiment 1：Nitric acid, remaining technical process are replaced with 20g sodium nitrites
And Parameter Conditions are same as Example 1.
It is calculated through weighing, the weight that the present embodiment obtains industrial molybdenum oxide is 36.3g, and molybdenum oxygenation efficiency is 99.2%.
Comparative example 1
The present embodiment the difference is that only with embodiment 1：Nitric acid is not added, remaining technical process and Parameter Conditions are equal
It is same as Example 1.
It is calculated through weighing, the weight that the present embodiment obtains industrial molybdenum oxide is 46.6g, and molybdenum oxygenation efficiency is 37.1%.
Chemical element and object phase point are carried out to the industrial molybdenum oxide obtained in embodiment 1 to 5 and comparative example 1 and the first filtrate
Analysis, is as a result listed in Tables 1 and 2.
Chemical composition (the unit of 1 the produced industrial molybdenum oxide of the present invention of table：Weight percent, %)
2 present invention of table produces the chemical composition of the first filtrate
| Sample | Mo, g/L | Re, g/L | Cu, g/L | Fe, g/L | Volume, L |
| Embodiment 1 | 2.87 | 0.081 | 0.74 | 1.38 | 1 |
| Embodiment 2 | 2.52 | 0.074 | 0.65 | 1.45 | 1 |
| Embodiment 3 | 2.67 | 0.068 | 0.68 | 1.52 | 1 |
| Embodiment 4 | 2.62 | 0.076 | 0.78 | 1.26 | 1 |
| Embodiment 5 | 2.83 | 0.071 | 0.81 | 1.37 | 1 |
| Comparative example 1 | 2.85 | 0.045 | 0.76 | 1.45 | 1 |
By table 1 as it can be seen that major impurity Fe, Cu, Pb contents are all relatively low in the molybdic acid obtained in several embodiments, molybdic acid purity
It is higher, show that several embodiments of the method can obtain the preferable molybdic acid of quality.But in various embodiments, molybdenum oxygenation efficiency
Difference is very big, illustrates that the degree that molybdenum concntrate is aoxidized at different conditions is different.
As can be seen from Table 2, the filtrate obtained in several embodiments, is enriched main metallic element.Wherein, contain about 10%
Molybdenum and most rhenium, iron, copper etc..
From Tables 1 and 2 also it can be seen that, the addition of nitrogenous compound is in identical oxidizing condition such as pressure, temperature, reaction
Under time, the oxygenation efficiency of molybdenum and rhenium in molybdenum concntrate greatly improved.
Embodiment 6
The Low Grade Molybdenum Concentrates that the present embodiment need to be handled contain the various composition of following weight percent：Mo 42%, Re
0.8%, Cu 5%.The method of molybdenum, copper and rhenium includes the following steps in the present embodiment pressure oxidation separation Low Grade Molybdenum Concentrates：
Step 1: being ground to Low Grade Molybdenum Concentrates, 200 mesh sieve is then crossed, molybdenum concntrate powder is obtained, later will
50g molybdenum concntrate powder is added in deionized water, and the addition of the deionized water is 5 times of molybdenum concntrate powder quality, and mixing is equal
Ore pulp is obtained after even；
Step 2: ore pulp described in step 1, nitrogenous compound and sulfuric acid are added in autoclave pressure, then into reaction kettle
It is passed through oxygen, is 160 DEG C in temperature, pressure reacts 1h under conditions of being 1.0MPa, obtains slurry；The nitrogenous compound is nitre
Acid, the addition of the nitrogenous compound are the 10% of molybdenum concntrate powder quality, and the addition of the sulfuric acid is molybdenum concntrate powder
The 0.5% of quality；
Step 3: carrying out vacuum filter processing to slurry described in step 2, filter cake and the first filtrate are obtained；
Step 4: being washed to filter cake described in step 3 using deionized water, industrial molybdenum oxide is obtained after dry；It will
Washing lotion after washing merges with first filtrate, obtains mixed liquor, and then iron powder, iron filings or iron wire are added in mixed liquor,
The molal quantity of the iron powder, iron filings and iron wire is 1.05 times of copper molal quantity in Low Grade Molybdenum Concentrates, is filtered after stirring evenly,
Obtain filter residue and the second filtrate, later by filter residue melting copper, using in the second filtrate of ion exchange resin pair molybdenum and rhenium into
Row absorption, finally using the method recycling molybdenum and rhenium of substep desorption.
It is calculated through weighing, the weight that the present embodiment obtains industrial molybdenum oxide is 36.9g, and molybdenum oxygenation efficiency is 99.2%.
Embodiment 7
The Low Grade Molybdenum Concentrates that the present embodiment need to be handled contain the various composition of following weight percent：Mo 53%, Re
0.8%, Cu 0.5%.The method of molybdenum, copper and rhenium includes the following steps in the present embodiment pressure oxidation separation Low Grade Molybdenum Concentrates：
Step 1: being ground to Low Grade Molybdenum Concentrates, 200 mesh sieve is then crossed, molybdenum concntrate powder is obtained, later will
50g molybdenum concntrate powder is added in deionized water, and the addition of the deionized water is 20 times of molybdenum concntrate powder quality, and mixing is equal
Ore pulp is obtained after even；
Step 2: ore pulp described in step 1, nitrogenous compound and sulfuric acid are added in autoclave pressure, then into reaction kettle
It is passed through oxygen, is 180 DEG C in temperature, pressure reacts 1h under conditions of being 1.5MPa, obtains slurry；The nitrogenous compound is nitre
Acid, the addition of the nitrogenous compound are the 20% of molybdenum concntrate powder quality, and the addition of the sulfuric acid is molybdenum concntrate powder
The 2% of quality；
Step 3: carrying out vacuum filter processing to slurry described in step 2, filter cake and the first filtrate are obtained；
Step 4: being washed to filter cake described in step 3 using deionized water, industrial molybdenum oxide is obtained after dry；It will
Washing lotion after washing merges with first filtrate, obtains mixed liquor, and then iron powder, iron filings or iron wire are added in mixed liquor,
The molal quantity of the iron powder, iron filings and iron wire is 1.15 times of copper molal quantity in Low Grade Molybdenum Concentrates, is filtered after stirring evenly,
Obtain filter residue and the second filtrate, later by filter residue melting copper, using in the second filtrate of ion exchange resin pair molybdenum and rhenium into
Row absorption, finally using the method recycling molybdenum and rhenium of substep desorption.
It is calculated through weighing, the weight that the present embodiment obtains industrial molybdenum oxide is 36.8g, and molybdenum oxygenation efficiency is 99.1%.
In above example, by filter residue melting copper, using in the second filtrate of ion exchange resin pair molybdenum and rhenium carry out
It is all routine techniques that absorption and the method for using substep desorption, which recycle molybdenum and rhenium,.When it is implemented, can first to the second filtrate with
D296 ion exchange resin adsorbs, rear that molybdenum is first desorbed with 10% NaOH aqueous solutions, then rhenium is desorbed with 10% ammonium hydroxide, obtains molybdic acid
Ammonium salt solution and ammonium perrhenate solution；It is last it is concentrated, sour it is heavy after, ammonium molybdate and ammonium perrhenate are made respectively.
The above is only presently preferred embodiments of the present invention, is not imposed any restrictions to the present invention.It is every according to invention skill
Art essence still falls within technical solution of the present invention to any simple modification, change and equivalence change made by above example
Protection domain in.
Claims (6)
1. a kind of method of molybdenum, copper and rhenium in pressure oxidation separation Low Grade Molybdenum Concentrates, which is characterized in that this method includes following
Step：
Step 1: being ground to Low Grade Molybdenum Concentrates, 200 mesh sieve is then crossed, molybdenum concntrate powder is obtained, later by molybdenum essence
Miberal powder end is added in deionized water, obtains ore pulp after mixing；
Step 2: ore pulp described in step 1, nitrogenous compound and sulfuric acid are added in autoclave pressure, then it is passed through into reaction kettle
Oxygen is 150 DEG C in temperature, and pressure oxidation reaction 1h, obtains slurry under conditions of pressure is 1.0MPa~1.5MPa；
Step 3: carrying out vacuum filter processing to slurry described in step 2, filter cake and the first filtrate are obtained；
Step 4: being washed to filter cake described in step 3 using deionized water, industrial molybdenum oxide is obtained after dry；It will washing
Washing lotion afterwards merges with first filtrate, obtains mixed liquor, and then iron powder, iron filings or iron wire are added in mixed liquor, stirring
Filtering, obtains filter residue and the second filtrate, later by filter residue melting copper, using in the second filtrate of ion exchange resin pair after uniformly
Molybdenum and rhenium adsorbed, finally using the method recycling molybdenum and rhenium of substep desorption.
2. the method for molybdenum, copper and rhenium, feature in a kind of pressure oxidation separation Low Grade Molybdenum Concentrates according to claim 1
It is, the mass percentage of molybdenum is 42%~53% in Low Grade Molybdenum Concentrates described in step 1, the mass percentage of copper
It is 0.5%~5%, the mass percentage of rhenium is 0.1%~0.8%.
3. the method for molybdenum, copper and rhenium, feature in a kind of pressure oxidation separation Low Grade Molybdenum Concentrates according to claim 1
It is, the addition of deionized water described in step 1 is 5~20 times of molybdenum concntrate powder quality.
4. the method for molybdenum, copper and rhenium, feature in a kind of pressure oxidation separation Low Grade Molybdenum Concentrates according to claim 1
It is, nitrogenous compound described in step 2 is any one in nitric acid, potassium nitrate, sodium nitrate, potassium nitrite and sodium nitrite
Kind is two or more.
5. the method for molybdenum, copper and rhenium, feature in a kind of pressure oxidation separation Low Grade Molybdenum Concentrates according to claim 1
It is, the addition of nitrogenous compound described in step 2 is the 5%~40% of molybdenum concntrate powder quality, the addition of the sulfuric acid
Amount is the 0.5%~2% of molybdenum concntrate powder quality.
6. the method for molybdenum, copper and rhenium, feature in a kind of pressure oxidation separation Low Grade Molybdenum Concentrates according to claim 1
Be, the molal quantity of iron powder described in step 4, iron filings and iron wire be copper molal quantity in Low Grade Molybdenum Concentrates 1.05~
1.15 again.
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