CN105384195B - Method for recovering rhenium from molybdenum smelting waste acid - Google Patents
Method for recovering rhenium from molybdenum smelting waste acid Download PDFInfo
- Publication number
- CN105384195B CN105384195B CN201510928911.5A CN201510928911A CN105384195B CN 105384195 B CN105384195 B CN 105384195B CN 201510928911 A CN201510928911 A CN 201510928911A CN 105384195 B CN105384195 B CN 105384195B
- Authority
- CN
- China
- Prior art keywords
- rhenium
- concentration
- resin
- spent acid
- ammonia
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G47/00—Compounds of rhenium
- C01G47/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
The invention discloses a method for recovering rhenium from molybdenum smelting waste acid, and belongs to the technical field of metal rhenium recycling. The method comprises the following steps: 1) filtering molybdenum smelting waste acid, and adsorbing filtrate by a composite amino ethylene weak base type anion exchange resin column until adsorption is saturated; 2) desorbing with ammonia water after adsorption saturation, collecting desorption liquid, and evaporating and crystallizing to obtain ammonium perrhenate. The saturated adsorption capacity of the composite amino ethylene weak base type anion exchange resin to rhenium is large, the content of rhenium in desorption liquid is more than 100 times of that of rhenium in waste acid, and compared with the existing extraction method and ion exchange method, the recovery rate of rhenium is high and reaches more than 98%. And meanwhile, by utilizing the solubility difference of ammonium perrhenate, ammonium molybdate and ammonium sulfate and adopting evaporative crystallization operation to purify the ammonium perrhenate, the purity of the obtained ammonium perrhenate reaches more than 99.9 percent. The rhenium recovery process is simple, environment-friendly, simple and convenient to operate and suitable for large-scale production and application.
Description
Technical field
The present invention relates to a kind of smelt the method that rhenium is reclaimed in spent acid from molybdenum, belong to rhenium metal utilization technology field.
Background technology
Rhenium metal is a kind of rare refractory metal, industrially has important purposes.It is mainly used in petroleum reforming
Catalyst and superalloy, its consumption account for the 20% and 70% of rhenium product consumption respectively.As rhenium resource seldom has independent
Mineral deposit, more in the form of associated minerals, is distributed mainly in Chalkopyrite and molybdenite, therefore rhenium is mainly molybdenum ore, copper mine and exists
Side-product during exploitation.As rhenium oxide easily distils, in the smelting process of calcining molybdenum ore concentrate and copper mine, rhenium
Enter in washing smoke liquid, mainly reclaimed by way of ion exchange or extraction.Due to molybdenum smelt spent acid in containing molybdenum,
The foreign ions such as fluorine, silicon, complicated component are big to extraction interference, therefore reclaim the rhenium in molybdenum smelting spent acid using solvent extraction, return
Yield is not high, and Solvent quantity is big, complex operation, and Organic substance volatilization and abstraction waste liquor easily cause secondary pollution.Ion
Exchange process is to reclaim the effective ways that molybdenum smelts rhenium in spent acid, but the ion exchange resin of industrial application mostly is strong base at present
Anion exchange resin, the response rate are relatively low, and service life is short, need to frequently change, increased production cost；Stripping liquid is adopted simultaneously
With the sodium thiocyanate solution of high concentration, high cost and with toxicity.
The patent of invention of notification number CN102173457B is disclosed and a kind of ammonium perrhenate is prepared from the waste liquid containing molybdenum-rhenium
Method, including：To in the waste liquid containing molybdenum-rhenium, add hydrogen peroxide to solution be in yellow, add mixed agent (calcium hydroxide with
Calcium oxide is according to mass ratio 5:1 mixing) to solution pH value be 6～7, filter pressing separate；Filtrate is collected, filtrate is cloudy by weak base type
Ion exchange resin column (tertiary amine groups styrene series anion exchange column) carry out on post adsorb, when the concentration of rhenium in effluent it is constant
When stop absorption, use NH3·H2The eluent collected is heated concentration at 98～100 DEG C by O eluting, and cooling, crystallization obtain final product height
Rehenic acid ammonium product.The concentration enrichment of rhenium can be made to improve nearly 20 times using the method, the eluting rate of rhenium is more than 98%, and the response rate is more than
93%, the high purity more than 99.5% of ammonium perrhenate product.But its complex operation, the response rate of rhenium need to be carried
It is high.
The content of the invention
It is an object of the invention to provide a kind of smelt the method that rhenium is reclaimed in spent acid from molybdenum, its process is simple is easy to operate,
The response rate of rhenium is high.
In order to realize object above, the technical solution adopted in the present invention is：
It is a kind of that the method that rhenium is reclaimed in spent acid is smelted from molybdenum, comprise the following steps：
1) molybdenum is smelted spent acid to filter, the compound amido ethylene system weak base type anion-exchange resin column absorption of filtrate Jing, extremely
Adsorption saturation；
2) after adsorption saturation, solution with ammonia is inhaled, and collects stripping liquid, and evaporative crystallization obtains ammonium perrhenate.
Step 1) in molybdenum smelt spent acid be the flue gas that produces during oxidizing roasting of molybdenum concntrate Jing after spray, dedusting by spraying
Drench the spent acid that tower flows out.
Step 1) in molybdenum smelt spent acid before filtration, (such as in spent acid, sulfur, molybdenum, rhenium, fluorine etc. is dense can first to carry out chemical composition
Degree) analysis, to determine separating technology, and the yield to rhenium is estimated.
Step 1) in filter purpose be remove spent acid in solid particulate matter of the particle diameter more than 0.5 μm.Such as can be using double
Tub filter, in filter, more than 5 μm, the filter element aperture of filter element filtering component exists the filter sizes of cloth-bag type filter assemblies
More than 0.5 μm.
Step 1) in be combined amido ethylene system weak base type anion exchange resin and can adopt commercial goods, also can be on chlorine ball
Import mixing amine functionality to be obtained.Its preparation method is：Chlorine ball is placed in water swelling, addition methylamine, N, N- dimethyl
Aniline and Dimethylammonium chloride, the insulation reaction 4～10 hours at 60～90 DEG C of temperature, reaction is finished isolates resin, you can.Institute
Chlorine ball and methylamine, N are stated, accelerine, the mass ratio of Dimethylammonium chloride are 3:3～5:5～7:2～4.The weak base type it is cloudy from
Sub-exchange resin is that milky is spherical, 600～1200 μm of granularity, humidity 42%～47%, 660～700g/L of wet density.
The chlorine ball is the suspension polymerisation in water phase of styrene monomer and divinylbenzene monomer, and gained copolymer bead is (in vain
Ball) by chloromethylation, chloromethyl is imported on the phenyl ring of Archon and be obtained.The degree of cross linking of chlorine ball is 10%, is purchased from river
Northern Langfang electric power resin company limited.
Using front, compound amido ethylene system weak base type anion-exchange resin column need to be carried out at alkali cleaning, pickling and conversion
Reason, wherein alkali cleaning can adopt the NaOH solution of concentration 1%～10%, pickling and conversion processing can be respectively adopted concentration 1%～
10% hydrochloric acid or sulfuric acid solution, the consumption of above-mentioned solution are respectively 1～10 times of resin volume.Alkali cleaning-pickling-conversion process
Alkalescence and acid impurities that resin is mingled with process of production can be eliminated, while by the ion conversion that resin is carried being and spent acid phase
Same system, it is to avoid introduce the foreign ion on resin.
In practical application, being combined amido ethylene system weak base type anion-exchange resin column need to be at least provided with 3 group, with the side of series connection
Formula connects.
Step 1) in the flow velocity of filtrate be 1～3BV/h, after discontinuity detection is adsorbed in liquid during rhenium concentration control reaction
Between, when in liquid after absorption, rhenium concentration is equal to rhenium concentration in spent acid, resin column adsorption saturation.
Step 2) in desorbing using concentration 1%～10% ammonia (i.e. NH3The ammonia of content 1%～10%), ammonia
1～20 times for resin volume of consumption, flow velocity are 0.1～5BV/h.
Step 2) in collect stripping liquid Jing be evaporated to the 5%～30% of original volume, add hydrogen peroxide (it is commercially available,
Concentration 30%) and ammonia (commercially available, concentration 25%～28%), evaporative crystallization obtains final product ammonium perrhenate.The addition of hydrogen peroxide is dense
The 1%～20% of contracting liquid product, which act as making rhenium that highly charged ions are converted in evaporation and crystal process；The addition of ammonia
For the 1%～10% of the volume of concentrate, which has the amount of enough free ammonias in acting as keeping solution, make rhenium in evaporative crystallization mistake
The Cheng Zhongyou higher response rate and purity.
Step 2) in evaporative crystallization operation can carry out at twice, be evaporated to for the first time (stripping liquid) original volume 1%～
10%, (filtrate can return to be processed in spent acid again) is filtered, gained crystal carries out double evaporation-cooling crystallization Jing after water dissolution, to (molten
Liquid) original volume 1%～10%, filter (filtrate can return to be processed in stripping liquid again), obtain final product highly purified ammonium perrhenate.
Beneficial effects of the present invention：
The present invention is smelted in spent acid from molybdenum using compound amido ethylene system weak base type anion exchange resin and reclaims rhenium, to rhenium
Saturated extent of adsorption is big, and in stripping liquid, rhenium content is enriched with more than 100 times compared with rhenium content in spent acid, and compare existing extraction and from
Response rate height of the sub- exchange process to rhenium (up to more than 98%).Meanwhile, using ammonium perrhenate, ammonium molybdate, ammonium sulfate poor solubility
Different, using evaporative crystallization operation purification ammonium perrhenate, the purity of gained ammonium perrhenate is up to more than 99.9%.Rhenium recovery in the present invention
Process is simple, environmental protection, do not produce new pollutant (spent acid after absorption enters circulation neutralisation treatment), and operate letter
Just, it is suitable to large-scale production application.
The present invention reclaims rhenium using inverted compound amido ethylene system weak base type anion-exchange resin column, compares background
In technology, tertiary amine groups styrene series anion exchange resin has advantages below：1) resin has higher to rhenium under compared with highly acidity
Adsorption capacity, while making molybdenum-rhenium have higher distribution ratio, can save neutralization and filter pressing lock out operation, and shortened process is saved
Cost, while can also avoid rhenium from losing in neutralization, filter pressing separation process, improves the response rate of rhenium；2) rhenium content in stripping liquid
More than 100 times are enriched with compared with rhenium content in spent acid；3) resin long service life, commerical test is using three months performances without substantially declining
Subtract；4) there is preferable adsorption desorption performance to rhenium, the response rate of rhenium is more than 98% in ion exchange process.
Description of the drawings
Fig. 1 is the process flow diagram in embodiment 1 from recovery rhenium in molybdenum smelting spent acid.
Specific embodiment
Following embodiments are only described in further detail to the present invention, but do not constitute any limitation of the invention.
Embodiment 1
The method (process flow diagram is shown in Fig. 1) that rhenium is reclaimed in spent acid is smelted in the present embodiment from molybdenum, step is as follows：
1) 20L compound amido ethylene system weak base type anion exchange resin is respectively charged in 4 radical ion exchange columns (per root
Pillar loads 5L resins), and it is connected in series, first deionized water cleans resin, then successively with the NaOH of 60L concentration 10%, dense
The HCl cleanings of degree 10%, finally with the H of 100L concentration 5%2SO4Resin is converted, it is standby；
The preparation method of compound amido ethylene system weak base type anion exchange resin is：By chlorine ball (purchased from Langfang in Hebei Province's electricity
Power resin company limited) be placed in water swelling 1 hour after leach, add mass ratio 3:4:6:3 methylamine, N, accelerine
And Dimethylammonium chloride, the insulation reaction 7 hours at 75 DEG C of temperature, reaction are finished and leach resin, soak, make immersion in dilute hydrochloric acid
Solution is in faintly acid, obtains final product milky spherical resin, and the granularity of the resin is 900 μm, humidity 44.5%, wet density 680g/L；
2) taking molybdenum smelting spent acid carries out component analyses, measures S 49g/L, Mo 582mg/L, Re 48mg/L, F in acid solution
Spent acid is squeezed into double barrels type accurate filter (purchased from the limited public affairs of the large environmental protection equipment of Suzhou City of Jiangsu Province gold with acid-proof pump by 12.1g/L
Department), to remove solid particulate matter of the particle diameter more than 0.5 μm in spent acid, wherein the filter sizes of cloth-bag type filter element are at 5 μm
More than, the filter element aperture of filter element filtering component is more than 0.5 μm；
3) the spent acid peristaltic pump after filtration is imported into ion exchange column with the flow velocity of 3BV/h, it is every in ion exchange process
The concentration of rhenium in liquid after absorption is detected every 2h, when the concentration of rhenium in liquid after No. 1 post absorption is equal to rhenium concentration in spent acid, that is, is thought
No. 1 post reaches saturated adsorption capacity, and No. 1 post stops adsorbing and carrying out desorption, and spent acid imports No. 4 posts from No. 2 posts and derives, and treats 2
The absorption of number post is finished, and No. 1 post desorbing is finished, and after No. 1 post is come No. 4 posts, spent acid imports No. 1 posts from No. 3 posts and derives, with this
Analogize；The concentration of rhenium in liquid after adsorbing is determined, the adsorption rate for obtaining rhenium is 98.76%；
4) resin that first deionized water is cleaned in No. 1 post, then with the ammonia desorbing of 20L concentration 5%, ammonia flow rate is
1BV/h, obtains 20L stripping liquids, and the concentration for determining rhenium in stripping liquid is 5.27g/L, and the desorption efficiency for obtaining rhenium is 99.54%；
5) stripping liquid is placed in rotary evaporator and is evaporated to 4L, add after taking-up 400mL concentration 30% hydrogen peroxide and
The ammonia of 500mL concentration 25%, is placed in water-bath and is evaporated to 1.5L, filters, and filtrate is returned in spent acid, and the white crystal for obtaining is used
2L deionized water dissolving, re-evaporation to 200mL are filtered, and filtrate is returned in stripping liquid, the white crystal drying for obtaining, and obtain final product height
Rehenic acid ammonium, purity 99.976%；
6) ibid, the response rate and purity of ammonium perrhenate is suitable for remaining resin column operation.
Embodiment 2
The method that rhenium is reclaimed in spent acid is smelted in the present embodiment from molybdenum, step is as follows：
1) 20L compound amido ethylene system weak base type anion exchange resin is respectively charged in 4 radical ion exchange columns (per root
Pillar loads 5L resins), and be connected in series, first deionized water cleans resin, then successively with the NaOH of 80L concentration 8%, concentration
8% HCl cleanings, finally with the H of 80L concentration 8%2SO4Resin is converted, it is standby；
The preparation method of compound amido ethylene system weak base type anion exchange resin is：By chlorine ball (purchased from Langfang in Hebei Province's electricity
Power resin company limited) be placed in water swelling 1 hour after leach, add mass ratio 3:5:5:4 methylamine, N, accelerine
And Dimethylammonium chloride, insulation reaction 10 hours under temperature 60 C, reaction finish and leach resin, soak, make leaching in dilute hydrochloric acid
Bubble solution is in faintly acid, obtains final product milky spherical resin, and the granularity of the resin is 600 μm, humidity 42%, wet density 660g/L；
2) taking molybdenum smelting spent acid carries out component analyses, measures S 56g/L, Mo 634mg/L, Re 54mg/L, F in acid solution
Spent acid is squeezed into double barrels type accurate filter (with embodiment 1) with acid-proof pump by 11.5g/L, to remove the solid particle in spent acid,
, more than 5 μm, the filter element aperture of filter element filtering component is more than 0.5 μm for the wherein filter sizes of cloth-bag type filter element；
3) the spent acid peristaltic pump after filtration is imported into ion exchange column with the flow velocity of 1.5BV/h, in ion exchange process
The concentration of rhenium in liquid after absorption is detected every 2h, when the concentration of rhenium in liquid after No. 1 post absorption is equal to rhenium concentration in spent acid, that is, is recognized
Saturated adsorption capacity is reached for No. 1 post, No. 1 post stops adsorbing and carrying out desorption, and spent acid imports No. 4 posts from No. 2 posts and derives, treats
No. 2 post absorption are finished, and No. 1 post desorbing is finished, and after No. 1 post is come No. 4 posts, spent acid imports No. 1 post from No. 3 posts and derives, with
This analogizes；The concentration of rhenium in liquid after adsorbing is determined, the adsorption rate for obtaining rhenium is 99.32%；
4) resin that first deionized water is cleaned in No. 1 post, then with the ammonia desorbing of 25L concentration 3%, ammonia flow rate is
0.5BV/h, obtains 25L stripping liquids, and the concentration for determining rhenium in stripping liquid is 5.08g/L, and the desorption efficiency for obtaining rhenium is 99.74%；
5) stripping liquid is placed in rotary evaporator and is evaporated to 3L, add after taking-up 300mL concentration 30% hydrogen peroxide and
The ammonia of 400mL concentration 25%, is placed in water-bath and is evaporated to 2L, filters, and filtrate is returned in spent acid, the white crystal 2L for obtaining
Deionized water dissolving, re-evaporation to 150mL are filtered, and filtrate is returned in stripping liquid, the white crystal drying for obtaining, and obtain final product high rhenium
Sour ammonium, purity 99.985%；
6) ibid, the response rate and purity of ammonium perrhenate is suitable for remaining resin column operation.
Embodiment 3
The method that rhenium is reclaimed in spent acid is smelted in the present embodiment from molybdenum, step is as follows：
1) 20L compound amido ethylene system weak base type anion exchange resin is respectively charged in 4 radical ion exchange columns (per root
Pillar loads 5L resins), and it is connected in series, first deionized water cleans resin, then successively with the NaOH of 100L concentration 5%, dense
The HCl cleanings of degree 5%, finally with the H of 60L concentration 10%2SO4Resin is converted, it is standby；
The preparation method of compound amido ethylene system weak base type anion exchange resin is：By chlorine ball (purchased from Langfang in Hebei Province's electricity
Power resin company limited) be placed in water swelling 1 hour after leach, add mass ratio 3:3:7:2 methylamine, N, accelerine
And Dimethylammonium chloride, the insulation reaction 4 hours at 90 DEG C of temperature, reaction are finished and leach resin, soak, make immersion in dilute hydrochloric acid
Solution is in faintly acid, obtains final product milky spherical resin, and the granularity of the resin is 1200 μm, humidity 47%, wet density 700g/L；
2) taking molybdenum smelting spent acid carries out component analyses, measures S 58g/L, Mo 726mg/L, Re 59mg/L, F in acid solution
Spent acid is squeezed into double barrels type accurate filter (with embodiment 1) with acid-proof pump by 11.4g/L, to remove the solid particle in spent acid,
, more than 5 μm, the filter element aperture of filter element filtering component is more than 0.5 μm for the wherein filter sizes of cloth-bag type filter element；
3) the spent acid peristaltic pump after filtration is imported into ion exchange column with the flow velocity of 5BV/h, it is every in ion exchange process
The concentration of rhenium in liquid after absorption is detected every 2h, when the concentration of rhenium in liquid after No. 1 post absorption is equal to rhenium concentration in spent acid, that is, is thought
No. 1 post reaches saturated adsorption capacity, and No. 1 post stops adsorbing and carrying out desorption, and spent acid imports No. 4 posts from No. 2 posts and derives, and treats 2
The absorption of number post is finished, and No. 1 post desorbing is finished, and after No. 1 post is come No. 4 posts, spent acid imports No. 1 posts from No. 3 posts and derives, with this
Analogize；The concentration of rhenium in liquid after adsorbing is determined, the adsorption rate for obtaining rhenium is 98.71%；
4) resin that first deionized water is cleaned in No. 1 post, then with the ammonia desorbing of 20L concentration 2.5%, ammonia flow rate is
1.5BV/h, obtains 20L stripping liquids, and the concentration for determining rhenium in stripping liquid is 5.14g/L, and the desorption efficiency for obtaining rhenium is 99.69%；
5) stripping liquid is placed in rotary evaporator and is evaporated to 2.5L, after taking-up, add the hydrogen peroxide of 400mL concentration 30%
With the ammonia of 500mL concentration 25%, it is placed in water-bath and is evaporated to 1.8L, filter, filtrate is returned in spent acid, the white crystal for obtaining
2L deionized water dissolving, re-evaporation to 100mL is used to filter, filtrate is returned in stripping liquid, the white crystal drying for obtaining is obtained final product
Ammonium perrhenate, purity 99.991%；
6) ibid, the response rate and purity of ammonium perrhenate is suitable for remaining resin column operation.
Embodiment 4
The method that rhenium is reclaimed in spent acid is smelted in the present embodiment from molybdenum, step is as follows：
1) 20L compound amido ethylene system weak base type anion exchange resin is respectively charged in 4 radical ion exchange columns (per root
Pillar loads 5L resins), and be connected in series, first deionized water cleans resin, then successively with the NaOH of 25L concentration 5%, concentration
5% HCl cleanings, finally with the H of 15L concentration 10%2SO4Resin is converted, it is standby；
The preparation method of compound amido ethylene system weak base type anion exchange resin is：By chlorine ball (purchased from Langfang in Hebei Province's electricity
Power resin company limited) be placed in water swelling 1 hour after leach, add mass ratio 3:5:7:3 methylamine, N, accelerine
And Dimethylammonium chloride, the insulation reaction 8 hours at 80 DEG C of temperature, reaction are finished and leach resin, soak, make immersion in dilute hydrochloric acid
Solution is in faintly acid, obtains final product milky spherical resin, and the granularity of the resin is 1100 μm, humidity 45%, wet density 690g/L；
2) taking molybdenum smelting spent acid carries out component analyses, measures S 58g/L, Mo 726mg/L, Re 59mg/L, F in acid solution
Spent acid is squeezed into double barrels type accurate filter (with embodiment 1) with acid-proof pump by 11.4g/L, to remove the solid particle in spent acid,
, more than 5 μm, the filter element aperture of filter element filtering component is more than 0.5 μm for the wherein filter sizes of cloth-bag type filter element；
3) the spent acid peristaltic pump after filtration is imported into ion exchange column with the flow velocity of 5BV/h, it is every in ion exchange process
The concentration of rhenium in liquid after absorption is detected every 2h, when the concentration of rhenium in liquid after No. 1 post absorption is equal to rhenium concentration in spent acid, that is, is thought
No. 1 post reaches saturated adsorption capacity, and No. 1 post stops adsorbing and carrying out desorption, and spent acid imports No. 4 posts from No. 2 posts and derives, and treats 2
The absorption of number post is finished, and No. 1 post desorbing is finished, and after No. 1 post is come No. 4 posts, spent acid imports No. 1 posts from No. 3 posts and derives, with this
Analogize；The concentration of rhenium in liquid after adsorbing is determined, the adsorption rate for obtaining rhenium is 98.82%；
4) resin in first deionized water cleaning resin column, then with the ammonia desorbing of 20L concentration 2.5%, ammonia flow rate
For 1.5BV/h, 20L stripping liquids are obtained, the concentration for determining rhenium in stripping liquid is 5.10g/L, the desorption efficiency for obtaining rhenium is
99.46%；
5) stripping liquid is placed in rotary evaporator and is evaporated to 2.5L, after taking-up, add the hydrogen peroxide of 400mL concentration 30%
With the ammonia of 500mL concentration 25%, it is placed in water-bath and is evaporated to 1.8L, filter, filtrate is returned in spent acid, the white crystal for obtaining
2L deionized water dissolving, re-evaporation to 100mL is used to filter, filtrate is returned in stripping liquid, the white crystal drying for obtaining is obtained final product
Ammonium perrhenate, purity 99.981%；
6) ibid, the response rate and purity of ammonium perrhenate is suitable for remaining resin column operation.
In other embodiments of the invention, when the concentration of rhenium in pending spent acid is relatively low, or the amount of pending spent acid
When less, the quantity of compound amido ethylene system weak base type anion-exchange resin column can be reduced as one sees fit, such as adopt 1 or 2；When
In spent acid, rhenium concentration is higher, or spent acid amount it is larger when, the quantity of resin column can increase as one sees fit, unrestricted.
Comparative example
The method that rhenium is reclaimed in spent acid is smelted in this comparative example from molybdenum, step is as follows：
1) (every pillar loads 5L trees 20L strong basic type anion-exchange resin D201 to be respectively charged into 4 radical ion exchange columns
Fat), and be connected in series, first deionized water cleans resin, then uses the HCl of the NaOH of 60L concentration 10%, concentration 10% clear successively
Wash, finally with the H of 100L concentration 5%2SO4Resin is converted, it is standby；
2) taking molybdenum smelting spent acid carries out component analyses, measures S 49g/L, Mo 582mg/L, Re 48mg/L, F in acid solution
Spent acid is squeezed into double barrels type accurate filter with acid-proof pump by 12.1g/L, to remove the solid particle in spent acid, wherein cloth-bag type
, more than 5 μm, the filter element aperture of filter element filtering component is more than 0.5 μm for the filter sizes of filter element；
3) the spent acid peristaltic pump after filtration is imported into ion exchange column with the flow velocity of 3BV/h, it is every in ion exchange process
The concentration of rhenium in liquid after absorption is detected every 2h, when the concentration of rhenium in liquid after No. 1 post absorption is equal to rhenium concentration in spent acid, that is, is thought
No. 1 post reaches saturated adsorption capacity, and No. 1 post stops absorption, and spent acid is imported (ibid operate) from No. 2 posts；After measure absorption in liquid
The concentration of rhenium, the adsorption rate for obtaining rhenium are 90.21%；
4) resin that first deionized water is cleaned in No. 1 post, then with the ammonia desorbing of 20L concentration 5%, ammonia flow rate is
1BV/h, obtains 20L stripping liquids, and the concentration for determining rhenium in stripping liquid is 1.86g/L, and the desorption efficiency for obtaining rhenium is 98.25%；
5) stripping liquid is placed in rotary evaporator and is evaporated to 4L, add after taking-up 400mL concentration 30% hydrogen peroxide and
The ammonia of 500mL concentration 25%, is placed in water-bath and is evaporated to 1.5L, filters, and filtrate is returned in spent acid, and the white crystal for obtaining is used
2L deionized water dissolving, re-evaporation to 200mL are filtered, and filtrate is returned in stripping liquid, the white crystal drying for obtaining, and obtain final product height
Rehenic acid ammonium；
6) remaining resin column operation is ibid.
Claims (9)
- It is 1. a kind of that the method that rhenium is reclaimed in spent acid is smelted from molybdenum, it is characterised in that：Comprise the following steps：1) molybdenum is smelted spent acid to filter, the compound amido ethylene system weak base type anion-exchange resin column absorption of filtrate Jing is extremely adsorbed Saturation；The preparation method of the compound amido ethylene system weak base type anion exchange resin is：Chlorine ball is placed in water it is swelling, plus Enter methylamine, DMA and Dimethylammonium chloride, the insulation reaction 4～10 hours at 60～90 DEG C of temperature, reaction is finished Isolate resin, you can；The chlorine ball and methylamine, N, accelerine, the mass ratio of Dimethylammonium chloride are 3:3～5:5～ 7:2～4；2) after adsorption saturation, solution with ammonia is inhaled, and collects stripping liquid, and evaporative crystallization obtains ammonium perrhenate.
- 2. method according to claim 1, it is characterised in that：The compound amido ethylene system weak base type anion exchange tree Using alkali cleaning, pickling and conversion processing is front carried out, wherein alkali cleaning adopts the NaOH solution of concentration 1%～10%, pickling to fat post The hydrochloric acid or sulfuric acid solution of concentration 1%～10% are respectively adopted with conversion processing.
- 3. method according to claim 2, it is characterised in that：The consumption of each solution point in alkali cleaning, pickling and conversion processing Wei 1～10 times of resin volume.
- 4. method according to claim 1, it is characterised in that：Step 1) in filtrate flow velocity be 1～3BV/h, work as absorption Afterwards in liquid rhenium concentration be equal to spent acid in rhenium concentration when, resin column adsorption saturation.
- 5. method according to claim 1, it is characterised in that：Step 2) in desorbing using concentration 1%～10% ammonia.
- 6. method according to claim 5, it is characterised in that：The consumption of ammonia is 1～20 times of resin volume, and flow velocity is 0.1～5BV/h.
- 7. method according to claim 1, it is characterised in that：Step 2) in stripping liquid Jing after concentrating under reduced pressure, add dioxygen Water and ammonia, evaporative crystallization obtain final product ammonium perrhenate.
- 8. method according to claim 7, it is characterised in that：The addition of hydrogen peroxide for the volume of concentrate 1%～ 20%, the addition of ammonia is the 1%～10% of the volume of concentrate.
- 9. method according to claim 1, it is characterised in that：Step 2) in evaporative crystallization operation carry out at twice, first It is secondary to be evaporated to the 1%～10% of original volume, filter, gained crystal carries out double evaporation-cooling crystallization Jing after water dissolution, to original volume 1%～10%, filter, obtain final product highly purified ammonium perrhenate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510928911.5A CN105384195B (en) | 2015-12-11 | 2015-12-11 | Method for recovering rhenium from molybdenum smelting waste acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510928911.5A CN105384195B (en) | 2015-12-11 | 2015-12-11 | Method for recovering rhenium from molybdenum smelting waste acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105384195A CN105384195A (en) | 2016-03-09 |
| CN105384195B true CN105384195B (en) | 2017-03-29 |
Family
ID=55417037
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510928911.5A Active CN105384195B (en) | 2015-12-11 | 2015-12-11 | Method for recovering rhenium from molybdenum smelting waste acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105384195B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106148737B (en) * | 2016-07-06 | 2019-05-14 | 东华理工大学 | A method of recycling association rhenium resource from sandstone-type uranium mineralization with respect ground dipping uranium extracting process adsorption tail liquid |
| DE102016010977A1 (en) * | 2016-09-13 | 2018-03-15 | H.C. Starck Surface Technology and Ceramic Powders GmbH | Process for the preparation of ammonium perrhenate |
| CN107226880B (en) * | 2017-06-09 | 2019-04-12 | 中国地质科学院郑州矿产综合利用研究所 | Composite amino ethylene series weak-alkaline anion exchange resin and method for recovering rhenium from copper smelting waste acid |
| CN107519948B (en) * | 2017-08-09 | 2020-06-05 | 中国地质科学院郑州矿产综合利用研究所 | Composite amino weakly-alkaline anion exchange resin and method for recovering rhenium from arsenic sulfide slag leachate |
| CN108611496A (en) * | 2018-06-30 | 2018-10-02 | 王胜利 | A method of extracting rhenium from Copper making waste acid |
| CN109179506B (en) * | 2018-09-21 | 2021-01-01 | 中国地质科学院郑州矿产综合利用研究所 | Method for synergistically recovering rhenium and molybdenum from molybdenum concentrate roasting leacheate |
| CN109535474B (en) * | 2018-11-22 | 2021-11-09 | 中南大学 | Coated impregnating resin, preparation method thereof and application thereof in selective adsorption of rhenium in waste acid |
| CN109626414B (en) * | 2019-01-31 | 2021-06-08 | 广州大学 | Method for recovering thallium and rhenium from smelting waste acid |
| CN110002503A (en) * | 2019-03-08 | 2019-07-12 | 北京矿冶科技集团有限公司 | A kind of method of purification removing organic matter in rehenic acid ammonium |
| CN110846510B (en) * | 2019-12-19 | 2021-08-10 | 安徽工业大学 | Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid |
| CN113564389A (en) * | 2021-07-13 | 2021-10-29 | 中国地质科学院郑州矿产综合利用研究所 | Method for recovering rhenium from molybdenum smelting waste acid by using secondary amine impregnated resin |
| CN115072789B (en) * | 2022-08-08 | 2024-06-07 | 中国地质科学院郑州矿产综合利用研究所 | Preparation method of high-purity ammonium rhenate |
| CN117447007B (en) * | 2023-10-26 | 2024-10-18 | 湖北美辰环保股份有限公司 | Process for separating ammonium sulfate and ammonium phosphate from iron phosphate production wastewater |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0623051B2 (en) * | 1985-04-05 | 1994-03-30 | 住友化学工業株式会社 | Recovery method of rhenium |
| CN102173457B (en) * | 2011-02-22 | 2013-01-16 | 辽宁大学 | Method for preparing ammonium perrhenate from waste liquid containing molybdenum and rhenium |
| CN102703699B (en) * | 2012-06-26 | 2013-12-04 | 西部鑫兴金属材料有限公司 | Recycling method of acid waste liquid after treatment of high-lead rhenium-containing molybdenum concentrate |
-
2015
- 2015-12-11 CN CN201510928911.5A patent/CN105384195B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105384195A (en) | 2016-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105384195B (en) | Method for recovering rhenium from molybdenum smelting waste acid | |
| CN105293772A (en) | Method for recovering of rare earth and resource utilization of ammonia nitrogen from rare earth processing and smelting wastewater | |
| CN104355474A (en) | Technique for extracting copper ions from industrial wastewater | |
| CN104129831B (en) | Method for simultaneous removal and recovery of heavy metal ions and organic acid by using chelating resin | |
| CN105238933B (en) | It is a kind of from the method containing removing and reclaiming element mercury in sulfur dioxide flue gas | |
| CN103320613B (en) | Method for recovering cobalt nickel through electrolytic manganese industrial ion exchange method | |
| CN102173457A (en) | Method for preparing ammonium perrhenate from waste liquid containing molybdenum and rhenium | |
| CN108975556B (en) | Method for purifying and recovering aged phosphoric acid polishing solution | |
| CN102320629B (en) | Method for producing reagent grade sodium sulfate by using white carbon black mother solution | |
| CN106219658A (en) | The classification removal of a kind of heavy metals in industrial wastewater and recovery method | |
| CN104760998B (en) | A kind of tungsten recovery method of tungstenic solution based on discarded SCR denitration | |
| CN105174556A (en) | High-acidity high-iron heavy metal wastewater quality-divided resource recycling method | |
| CN107267772A (en) | A kind of method that platinum and rhenium are reclaimed in the platinum-rhenium reforming catalyst from aluminium base | |
| CN102417194A (en) | Deep magnesium removal method of chelating resin for extracting lithium from salt lake brine | |
| CN106947864B (en) | A kind of system and its processing method recycling heavy metal from discarded SCR catalyst | |
| CN105016368A (en) | Iron-containing aluminum chloride solution iron removal method | |
| CN103060555A (en) | Purification cadmium removal method of nickel cobalt solution containing cadmium | |
| CN114797171A (en) | Production device and production process for extracting lithium from brine by efficient adsorption method | |
| CN107226880A (en) | Composite amino ethylene series weak-alkaline anion exchange resin and method for recovering rhenium from copper smelting waste acid | |
| CN108611496A (en) | A method of extracting rhenium from Copper making waste acid | |
| CN114293033B (en) | Method for extracting vanadium from vanadium-containing carbonation leaching liquid and recycling vanadium precipitation residual liquid | |
| CN108218039A (en) | A kind of method of resin adsorption desorption-diffusion dialysis processing VA races element oxo-anions waste water | |
| CN107519948A (en) | Composite amino weakly-alkaline anion exchange resin and method for recovering rhenium from arsenic sulfide slag leachate | |
| CN110846510B (en) | Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid | |
| CN109097584A (en) | The technique of platinum rhenium aluminium is recycled in a kind of platinum rhenium dead catalyst from alumina supporter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20170113 Address after: Longhai West Road Central District 450006 Henan city of Zhengzhou province No. 328 Applicant after: Zhengzhou Institute of Mineral Utilization,Chinese Academy of Geological Science Applicant after: Luoyang Luanchuan Molybdenum Group Co., Ltd. Address before: Longhai Road 450000 Henan city of Zhengzhou province No. 328 Applicant before: Zhengzhou Institute of Mineral Utilization,Chinese Academy of Geological Science Applicant before: Luoyang Molybdenum Group Metal Material Co., Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |