CN107226880B - Composite amino ethylene series weak-alkaline anion exchange resin and method for recovering rhenium from copper smelting waste acid - Google Patents
Composite amino ethylene series weak-alkaline anion exchange resin and method for recovering rhenium from copper smelting waste acid Download PDFInfo
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- CN107226880B CN107226880B CN201710434010.XA CN201710434010A CN107226880B CN 107226880 B CN107226880 B CN 107226880B CN 201710434010 A CN201710434010 A CN 201710434010A CN 107226880 B CN107226880 B CN 107226880B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
Abstract
The invention relates to a composite amino ethylene series weak-alkaline anion exchange resin and a method for recovering rhenium from copper smelting waste acid, belonging to the technical field of metal rhenium recovery and utilization. The composite amino ethylene series weak-base anion exchange resin is prepared by the preparation method comprising the following steps: swelling polystyrene chloride balls in an organic solvent for 4-10 h, slowly adding a mixture of dicyclohexylamine, pyridine and N-methylcyclohexylamine, reacting at room temperature for 1-6 h, heating to 40-90 ℃, reacting for 6-18 h, and then carrying out vacuum filtration to obtain the polystyrene chloride ball. The composite amino ethylene weak-base anion exchange resin has good adsorption selectivity on low-concentration rhenium (2-10 mg/L) in waste acid with high acidity and high-concentration impurity ions, does not adsorb impurity ions, particularly toxic arsenate ions basically, and directly enters an ion exchange column after being filtered, so that the process is simplified, and the recovery rate of rhenium is improved.
Description
Technical field
It is recycled the present invention relates to a kind of compound amido ethylene system's weak-base anion-exchange resin and from Copper making spent acid
The method of rhenium belongs to rhenium metal utilization technology field.
Background technique
Rhenium metal has high-melting-point, high intensity, good plasticity and excellent mechanical stability, is aircraft engine turbine
Indispensable element in blade, therefore there is very high value.Rhenium without independent mineral deposit, is mainly distributed in nature
In the molybdenite and chalcopyrite of porphyry Cu-Mo deposit, rhenium-containing concentrate during pyrometallurgical smelting due to the sulfide oxidation of rhenium and
Generate volatile Re2O7Into flue gas, flue gas is in acid making system purification process, Re2O7HReO is generated into spent acid4, become
Mention the raw material of rhenium.Molybdenum smelts rhenium concentration in spent acid and is generally 50~500mg/L, in contrast, rhenium concentration is more in Copper making spent acid
It is low, generally 2~10mg/L, while containing the impurity elements such as a large amount of arsenic, copper, sulphur, fluorine, silicon in Copper making spent acid, impurity from
Sub- concentration is significantly larger than rhenium concentration, and wherein for sulphur concentration close to 100g/L, arsenic concentration is 2~10g/L.How the slave copper of economical and efficient
Smelt spent acid in recycling rhenium have very big technical difficulty, therefore from Copper making spent acid recycle rhenium do not cause it is enough heavy
Depending on making the resource eventually enter into neutralization slag and being discarded, not only caused the waste of secondary resource, but also polluted environment.
Application publication number discloses one kind for the Chinese invention patent of CN102628110A and recycles rhenium from Copper making spent acid
Method, thiosulfate is added in Copper making spent acid, filters decopper(ing) after reaction by including pre- decopper(ing), then will be thio
Sulfate is added in the decopper(ing) tail washings obtained after filtering, and rich rhenium concentrate is obtained by filtration after reaction.The method needs first to spent acid
Decopper(ing) processing is carried out, and need to heat and control reaction temperature at 40~100 DEG C, increases cost；Products obtained therefrom is rhenium content simultaneously
3%~20% rich rhenium concentrate is made and can sell to therefrom recycle rhenium wherein also containing the copper and arsenic more much higher than rhenium content
The ammonium perrhenate product sold, it is also necessary to complicated leaching and purification process.
Application publication number is that the Chinese invention patent of CN102502855A discloses one kind from copper blast furnace off-gas washing spent acid
The method that extraction prepares ammonium perrhenate in liquid, is included in spent acid and mixed organic solvents is added, and three stage countercurrent extractions are carried out under room temperature
It takes, coordination washing and pure water then is carried out to rhenium-containing load organic phases, then be stripped with ammonium hydroxide, in rhenium-containing strip liquor
Sec-octyl alcohol is added and removes organic phase, after obtained rhenium-containing strip liquor is stood 20h to faintly acid, extracted, washed again, instead
Extract and except organic phase operates, finally obtain the secondary rhenium-containing strip liquor of high concentration, finally crystallizes preparation grade with concentrated frozen and be greater than
98% ammonium perrhenate product.The process flow is complicated, needs to be extracted twice respectively, washs, is stripped, except organic phase is grasped
Make；Extractant used is volatile, toxic, produces new waste water and waste liquid in the process, is unfavorable for environmental protection.
Application publication number discloses one kind for the Chinese invention patent of CN103773963A and recycles rhenium from Copper making spent acid
Method, including by steam-coil-heater after Copper making spent acid is once filtered, then flocculant, thiosulfate is successively added
It is reacted, finally passes through secondary filter, obtaining filter residue is copper rhenium sediment.The process flow is simple, and the rate of recovery of rhenium is reachable
To 98% or more, but obtained product is the rich rhenium slag of rhenium content 2%~4%, wherein also containing 10%~20% copper,
2%~5% silver, 6%~10% bismuth, while the rate of deposition of arsenic about 10% is still needed to ammonium perrhenate product is made in rhenium
Want complicated separating-purifying process.
Application publication number discloses a kind of smelt in spent acid from molybdenum for the Chinese invention patent of CN105384195A and efficiently returns
The method for receiving rhenium, including filtering, are passed directly into the friendship equipped with compound amido ethylene system weak-base anion-exchange resin for spent acid
It changes column to be adsorbed, then solution with ammonia is inhaled, and evaporative crystallization prepares ammonium perrhenate product.But compared with molybdenum smelts spent acid, copper
It is higher to smelt rhenium concentration lower (2~10mg/L), impurity ion content in spent acid, therefore, above-mentioned smelt in spent acid from molybdenum is recycled
The method of rhenium is not suitable for Copper making spent acid.
In conclusion developing, a kind of simple process, at low cost, gained perrhenate product purity is high from Copper making spent acid
The method of middle recycling rhenium is extremely urgent.
Summary of the invention
The purpose of the present invention is to provide a kind of compound amido ethylene system weak-base anion-exchange resins, and the resin is to copper
The rhenium smelted in spent acid has good adsorption effect.
The present invention second is designed to provide a kind of using above-mentioned compound amido ethylene system's weakly-basic anion exchange tree
The method that rouge recycles rhenium from Copper making spent acid, to solve to recycle from Copper making spent acid in the prior art, rhenium is at high cost, technique
Complicated, gained rhenium-containing the technical issues of product purity is low.
To achieve the above object, the technical scheme is that
A kind of compound amido ethylene system weak-base anion-exchange resin, is made by method comprising the following steps: will be gathered
Styrene chlorine ball is swollen 4~10h in organic solvent, is then slowly added into the mixing of dicyclohexyl amine, pyridine, N-methylcyclohexylamine
Object, at room temperature react 1~6h after, be warming up to 40~90 DEG C of 6~18h of reaction, be filtered by vacuum later to get；The polystyrene
Chlorine ball, dicyclohexyl amine, pyridine and N-methylcyclohexylamine mass ratio be 3:3~9:1~4:2~6.
The polystyrene chlorine ball is before swelling through dehydrated alcohol extracting, drying and processing.The extracting is in Soxhlet extraction
It is carried out in device.The extraction times are 10h.The mass ratio of the polyethylene chlorine ball and dehydrated alcohol is 1:3~8.The baking
Dry temperature is 40 DEG C.
Above-mentioned organic solvent is N,N-dimethylformamide, dimethyl sulfoxide, any one in N-Methyl pyrrolidone.
The mass ratio of above-mentioned polystyrene chlorine ball and organic solvent is 1:2~5.
The polystyrene chlorine ball is the suspension polymerisation in water phase of styrene monomer and divinylbenzene monomer, gained copolymer
It is obtained by chloromethylation.Chlorinity is 18% in the polystyrene chlorine ball, the degree of cross linking 6%.Used in the present invention
The polystyrene chlorine ball degree of cross linking is low, improves the rate of adsorption of the rhenium on resin, spent acid is inhaled under higher flow velocity
It is attached.
The polystyrene chlorine ball is purchased from Zhengguang Resin Co., Ltd..
Above-mentioned compound amido ethylene system's weak-base anion-exchange resin is that milky is spherical, 700~1400 μm of granularity, wet
Degree 40%~45%, 600~680g/L of wet density.
It is a kind of that rhenium is recycled from Copper making spent acid using above-mentioned compound amido ethylene system's weak-base anion-exchange resin
Method, comprising the following steps: 1) Copper making spent acid is flowed through and be filled with compound amido ethylene system weak-base anion-exchange resin
Ion exchange column absorption；2) it is desorbed with sodium hydroxide solution, collects stripping liquid, stripping liquid obtains potassium perrhenate through evaporative crystallization.
Copper making spent acid is the flue gas that generates in pyrogenic process roasting process of copper concentrate through spray, dedusting, cooling in step 1)
Spent acid by being flowed out in spray column afterwards.
The ingredient of the Copper making spent acid includes S, Re, As, F.
Copper making spent acid is before flowing through adsorption column through filtration treatment in step 1).
The purpose of above-mentioned filtering is to remove solid particulate matter of the partial size at 1 μm or more in spent acid.Above-mentioned filtering is preferably adopted
Use Gore filter.Wherein the filter sizes of filter bag are at 1 μm or more.Above-mentioned Gore filter is purchased from W. L. Gore & Associates, Inc. company.
Compound amido ethylene system's weak-base anion-exchange resin handles before using through pre-swollen and conversion processing.
Pre-swollen processing use mass fraction for 1%~30% NaCl solution；The conversion processing uses quality
The sulfuric acid solution that score is 1%~30%.
The NaCl solution, the volume of sulfuric acid solution are 1~20 times of the anion exchange resin volume.Pre-swollen
Processing is to expand the volume of resin completely, and aperture fully opens, to increase the specific surface area of ion-exchange reactions；Turn
Change processing is in order to convert ionic type identical with spent acid system for the ionic type carried on resin functionality, to keep away
Exempt to introduce other impurities ion.
The flow velocity of spent acid is 2~20BV/h in step 1).
Hydrogen is used after the above-mentioned ion exchange column adsorption saturation for being filled with compound amido ethylene system weak-base anion-exchange resin
Sodium hydroxide solution desorption.Resin column adsorption saturation when the concentration of rhenium is equal to the concentration of rhenium in spent acid in solution after the absorption.
The ion exchange column of compound amido ethylene system weak-base anion-exchange resin is filled in step 1) in use process
Middle setting four or more, connects, last root is spare in a series arrangement.Filtered spent acid is flowed into from first pillar, from
Second pillar outflow of number；At regular intervals respectively to the efflux sampling analysis of the exchange column used, when first pillar
When rhenium concentration is equal to rhenium concentration in spent acid in efflux, it is believed that first pillar saturation desorbs first pillar, spent acid
It flows into from second, is flowed out from last root；When rhenium concentration is equal to rhenium concentration in spent acid in second pillar efflux, it is believed that
Second pillar adsorption saturation, first pillar desorption finishes at this time, and spent acid is flowed into from third root pillar, from first pillar stream
Out；So circulation.
The mass fraction of sodium hydroxide solution is 5%~30% in step 2).Strippant uses strong electrolyte sodium hydroxide
Solution effectively raises desorption efficiency.
The flow velocity of sodium hydroxide solution is 1~20BV/h in step 2)；The volume of sodium hydroxide solution used is serotonin
0.5~10 times of base ethylene system weak-base anion-exchange resin volume.
Evaporative crystallization is that stripping liquid is evaporated to the 1%~30% of original volume under vacuum conditions in step 2), is then existed
KOH is added under thermosol state, is placed in cooling in freezer and obtains potassium perrhenate crystal.The evaporation carries out to mention under vacuum conditions
High evaporation efficiency.
The molar ratio of the KOH and rhenium in stripping liquid is 0.5~3:1.
It is filtered after evaporative crystallization in step 2) up to potassium perrhenate.Filtrate can return in spent acid and be adsorbed again.
The beneficial effects of the present invention are:
The synthesis material of compound amido ethylene of the invention system weak-base anion-exchange resin is common drug, cost
It is low, while gained resin has good adsorptivity to rhenium.
The present invention recycles the side of rhenium using compound amido ethylene system's weak-base anion-exchange resin from Copper making spent acid
Method makes spent acid be directly entered ion exchange column, eliminates spent acid N-process or dedoping step, simplifies process, avoids simultaneously
Loss of the rhenium in N-process；Resin used is especially virose arsenate ion to foreign ion and does not adsorb substantially,
There is good adsorptive selectivity to rhenium, while also there is excellent desorption performance, stripping liquid uses cheap sodium hydroxide
Solution can desorb completely rhenium from resin.
The present invention, using the concatenated mode of ion exchange column, both can guarantee from the method for recycling rhenium in Copper making spent acid
Resin can adsorb completely, and reduce the loss of rhenium in efflux, so that the rate of recovery of rhenium be made to be maintained at 97% or more, and inhale
Attached spent acid can be directly entered the wastewater treatment working section of smeltery, not generate new waste water and waste liquid, and the feature of environmental protection is good.
The method of present invention high efficiente callback rhenium from Copper making spent acid, is evaporated crystallization under vacuum conditions, improves
Evaporation efficiency, while liquid may be implemented to recycle after evaporation, lose rhenium not substantially in the process, while perrhenic acid is made
Potassium product purity is greater than 99.9%.
Detailed description of the invention
Fig. 1 is the process flow diagram that rhenium is recycled from Copper making spent acid.
Specific embodiment
Embodiments of the present invention are described further with reference to the accompanying drawing.
Embodiment 1
The present embodiment compound amido ethylene system weak-base anion-exchange resin, is made by method comprising the following steps:
By polystyrene chlorine ball in Soxhlet extractor with dehydrated alcohol extract 10h, then 40 DEG C drying, polystyrene chlorine ball with it is anhydrous
The mass ratio of ethyl alcohol is 1:3；By the polystyrene chlorine ball after drying, swelling 5 is small in N,N-dimethylformamide at room temperature
When, it is then slowly added into the mixture of dicyclohexyl amine, pyridine, N-methylcyclohexylamine, after reacting 2 hours at room temperature, is slowly heated up
The reaction was continued after to 50 DEG C 8 hours, drains mother liquor after reaction, and vacuum filtration obtains resin；Wherein polystyrene chlorine ball with
The mass ratio of n,N-Dimethylformamide is 1:2, the quality of polystyrene chlorine ball and dicyclohexyl amine, pyridine, N-methylcyclohexylamine
Than for 3:3:1:3.The granularity of compound amido ethylene system weak-base anion-exchange resin obtained by the present embodiment is 800 μm, humidity
40%, wet density 620g/L.
The method that the present embodiment recycles rhenium from Copper making spent acid, as shown in Figure 1, comprising the following steps:
1) the above-mentioned compound amido ethylene system weak-base anion-exchange resin of 140L is respectively charged into 4 radical ion exchange columns
(every pillar is packed into 35L resin), and be connected in series, resin first is cleaned with deionized water, then passes to 700L concentration 15%
NaCl solution makes the abundant pre-swollen of resin, then is passed through the H of 560L concentration 15%2SO4Solution converts resin, spare；
2) Copper making spent acid is taken to carry out constituent analysis, it is 5.74mg/L, As that measure S concentration in spent acid, which be 92g/L, Re concentration,
Concentration is that 896mg/L, F concentration are 2.68g/L, and spent acid is squeezed into Gore filter (purchased from W. L. Gore & Associates, Inc. company) with acid-proof pump,
To remove, partial size is in 1 μm or more of solid particulate matter in spent acid, and wherein the aperture of filter bag is at 1 μm or more；
3) 4 radical ion exchange columns are used in series, last root is spare, by filtered spent acid constant flow pump with 7BV/h's
Flow velocity imports No. 1 ion exchange column, flows out from No. 3 ion exchange columns, in ion exchange process after 4h detection absorption in liquid
The concentration of rhenium, after absorption carries out 144h, rhenium concentration stops absorption, to No. 1 close to the rhenium concentration in spent acid in No. 1 column efflux
Column is desorbed, and the adsorption rate that rhenium is obtained by the concentration of rhenium in No. 3 column effluxes of measurement is 98.96%；Then spent acid is from No. 2
Column flows into No. 4 column outflows, and to No. 2 column adsorption saturations, No. 1 column desorption is finished, and after No. 1 column is come No. 4 columns, spent acid is from No. 3
Column flows into No. 1 column outflow, and so on；Desorption is carried out to the resin in No. 1 column method particularly includes: first clear with deionized water
Resin is washed, then is passed through the sodium hydroxide solution that 100L mass fraction is 15% and desorbs, sodium hydroxide solution flow velocity is 6BV/h, is obtained
Into stripping liquid, rhenium concentration is 2793mg/L, compared with 487 times of rhenium concentration enrichment in spent acid；Stripping liquid is placed in vacuum evaporation apparatus
It is evaporated to 14L, KOH additional amount is 91g under thermosol state, is placed in freezer and crystallizes, obtained white crystal is perrhenic acid
Potassium, purity 99.94%；Filtrate returns in spent acid and re-starts absorption；
4) the adsorption and desorption operation of remaining resin column is same as above, the rate of recovery and purity and the phase in step 3) of potassium perrhenate
When.
Embodiment 2
The present embodiment compound amido ethylene system weak-base anion-exchange resin, by the preparation method system included the following steps
: by polystyrene chlorine ball in Soxhlet extractor with dehydrated alcohol extract 10h, 40 DEG C drying, polystyrene chlorine ball with it is anhydrous
The mass ratio of ethyl alcohol is 1:5, the polystyrene chlorine ball after drying is swollen 6 hours in dimethyl sulfoxide at room temperature, then
It is slowly added to the mixture of dicyclohexyl amine, pyridine, N-methylcyclohexylamine, after reacting 4 hours at room temperature, after being to slowly warm up to 70 DEG C
The reaction was continued 10 hours, and after reaction, vacuum filtration obtains resin；Wherein, the matter of polystyrene chlorine ball and dimethyl sulfoxide
For amount than being 1:3, polystyrene chlorine ball and the mass ratio of dicyclohexyl amine, pyridine, N-methylcyclohexylamine are 3:6:2:4.The present embodiment
The granularity of gained compound amido ethylene system weak-base anion-exchange resin is 900 μm, humidity 43%, wet density 640g/L.
The method that the present embodiment recycles rhenium from Copper making spent acid, comprising the following steps:
1) the above-mentioned compound amido ethylene system weak-base anion-exchange resin of 140L is respectively charged into 4 radical ion exchange columns
(every pillar is packed into 35L resin), and be connected in series, resin first is cleaned with deionized water, then passes to 700L concentration 10%
NaCl solution makes the abundant pre-swollen of resin, then is passed through the H of 700L concentration 10%2SO4Solution converts resin, spare；
2) take Copper making spent acid carry out constituent analysis, measure S concentration in spent acid be 104g/L, Re concentration be 2.84mg/L,
As concentration is that 1254mg/L, F concentration are 3.75g/L, and spent acid is squeezed into Gore filter with acid-proof pump, to remove partial size in spent acid
In 1 μm or more of solid particulate matter, wherein the aperture of filter bag is at 1 μm or more；
3) 4 radical ion exchange columns are used in series, last root is spare, by filtered spent acid constant flow pump with 8BV/h's
Flow velocity imports No. 1 ion exchange column, flows out from No. 3 columns, detects the concentration of rhenium in liquid after absorption in ion exchange process every 4h,
After absorption carries out 122h, rhenium concentration stops absorption, solves to No. 1 column close to the rhenium concentration in spent acid in No. 1 column efflux
It inhales, the adsorption rate that rhenium is obtained by the concentration of rhenium in No. 3 column effluxes of measurement is 98.03%；Then spent acid flows into 4 from No. 2 columns
The outflow of number column, to No. 2 column adsorption saturations, No. 1 column desorption is finished, and after No. 1 column is come No. 4 columns, spent acid flows into 1 from No. 3 columns
The outflow of number column, and so on；Desorption is carried out to the resin in No. 1 column method particularly includes: resin first is cleaned with deionized water,
It is passed through the sodium hydroxide solution desorption of 90L mass fraction 20% again, sodium hydroxide solution flow velocity is 4BV/h, is obtained in stripping liquid
Rhenium concentration is 2129mg/L, compared with 750 times of rhenium concentration enrichment in spent acid；Stripping liquid is placed in vacuum evaporation apparatus and is evaporated to 20L,
KOH additional amount is 63g under thermosol state, is placed in freezer and crystallizes, obtained white crystal is potassium perrhenate, and purity is
99.96%；Filtrate returns in spent acid and re-starts absorption；
4) the adsorption and desorption operation of remaining resin column is same as above, the rate of recovery and purity and the phase in step 3) of potassium perrhenate
When.
Embodiment 3
The present embodiment compound amido ethylene system weak-base anion-exchange resin is made by following preparation method: will be gathered
Styrene chlorine ball extracts 10h, 40 DEG C of drying, the matter of polystyrene chlorine ball and dehydrated alcohol with dehydrated alcohol in Soxhlet extractor
Polystyrene chlorine ball after drying is swollen 8 hours in N-Methyl pyrrolidone, then slowly by amount at room temperature than being 1:8
The mixture of dicyclohexyl amine, pyridine, N-methylcyclohexylamine is added, after reacting 6 hours at room temperature, continues after being to slowly warm up to 80 DEG C
Reaction 12 hours, after reaction, vacuum filtration obtain resin；The mass ratio of polystyrene chlorine ball and N-Methyl pyrrolidone is
1:5, polystyrene chlorine ball and the mass ratio of dicyclohexyl amine, pyridine, N-methylcyclohexylamine are 3:8:3:6.It is multiple obtained by the present embodiment
The granularity for closing amido ethylene system weak-base anion-exchange resin is 1100 μm, humidity 44%, wet density 660g/L.
The method that the present embodiment recycles rhenium from Copper making spent acid, comprising the following steps:
1) the above-mentioned compound amido ethylene system weak-base anion-exchange resin of 140L is respectively charged into 4 radical ion exchange columns
(every pillar is packed into 35L resin), and be connected in series, resin first is cleaned with deionized water, then passes to 980L concentration 5%
NaCl solution is swollen resin sufficiently, then is passed through the H of 840L concentration 5%2SO4Solution converts resin, spare；
2) Copper making spent acid is taken to carry out constituent analysis, it is 6.45mg/L, As that measure S concentration in spent acid, which be 87g/L, Re concentration,
Concentration is that 956mg/L, F concentration are 3.14g/L, and spent acid is squeezed into Gore filter with acid-proof pump, to remove in spent acid partial size 1
μm or more solid particulate matter, wherein the aperture of filter bag is at 1 μm or more；
3) 4 radical ion exchange columns are used in series, last root is spare, by filtered spent acid constant flow pump with 9BV/h's
Flow velocity imports No. 1 ion exchange column, flows out from No. 3 ion exchange columns, in ion exchange process after 4h detection absorption in liquid
The concentration of rhenium, after absorption carries out 96h, rhenium concentration stops absorption, to No. 1 column close to the rhenium concentration in spent acid in No. 1 column efflux
It is desorbed, the adsorption rate that rhenium is obtained by the concentration of rhenium in No. 3 column effluxes of measurement is 97.46%；Then spent acid is from No. 2 columns
The outflow of No. 4 columns is flowed into, to No. 2 column adsorption saturations, No. 1 column desorption is finished, and after No. 1 column is come No. 4 columns, spent acid is from No. 3 columns
No. 1 column outflow is flowed into, and so on；Desorption is carried out to the resin in No. 1 column method particularly includes: first cleaned with deionized water
Resin, then it is passed through the sodium hydroxide solution desorption of 120L mass fraction 10%, sodium hydroxide solution flow velocity is 3BV/h, is solved
Rhenium concentration is 2469mg/L in imbibition, compared with 383 times of rhenium concentration enrichment in spent acid；Stripping liquid is placed in vacuum evaporation apparatus and is evaporated
To 25L, KOH additional amount is 96g under thermosol state, is placed in freezer and crystallizes, and filtrate returns in stripping liquid, obtained white crystal
As potassium perrhenate, purity 99.98%；Filtrate returns in spent acid and re-starts absorption；
4) the adsorption and desorption operation of remaining resin column is same as above, the rate of recovery and purity and the phase in step 3) of potassium perrhenate
When.
Embodiment 4
The present embodiment compound amido ethylene system weak-base anion-exchange resin, by the preparation method system included the following steps
: by polystyrene chlorine ball in Soxhlet extractor with dehydrated alcohol extract 10h, 40 DEG C drying, polystyrene chlorine ball with it is anhydrous
The mass ratio of ethyl alcohol is 1:8, and the polystyrene chlorine ball after drying is swollen 4 hours in N-Methyl pyrrolidone at room temperature,
It is then slowly added into the mixture of dicyclohexyl amine, pyridine, N-methylcyclohexylamine, after reacting 1 hour at room temperature, is to slowly warm up to 90
The reaction was continued after DEG C 6 hours, is filtered by vacuum after reaction, obtains resin；Polystyrene chlorine ball and N-Methyl pyrrolidone
Mass ratio is 1:3, and polystyrene chlorine ball and the mass ratio of dicyclohexyl amine, pyridine, N-methylcyclohexylamine are 3:9:4:2.
The method that the present embodiment recycles rhenium from Copper making spent acid, comprising the following steps:
1) the above-mentioned compound amido ethylene system weak-base anion-exchange resin of 140L is respectively charged into 4 radical ion exchange columns
(every pillar is packed into 35L resin), and be connected in series, resin first is cleaned with deionized water, then passes to 980L concentration 1%
NaCl solution makes the abundant pre-swollen of resin, then is passed through the H2SO4 solution of 840L concentration 1% and converts to resin, spare；
2) Copper making spent acid is taken to carry out constituent analysis, it is 6.45mg/L, As that measure S concentration in spent acid, which be 87g/L, Re concentration,
Concentration is that 956mg/L, F concentration are 3.14g/L, and spent acid is squeezed into Gore filter with acid-proof pump, to remove in spent acid partial size 1
μm or more solid particulate matter, wherein the aperture of filter bag is at 1 μm or more；
3) 4 radical ion exchange columns are used in series, last root is spare, by filtered spent acid constant flow pump with 3BV/h's
Flow velocity imports No. 1 ion exchange column, flows out from No. 3 columns, detects the concentration of rhenium in liquid after absorption in ion exchange process every 4h,
After absorption carries out 96h, rhenium concentration stops absorption, desorbs to No. 1 column close to the rhenium concentration in spent acid in No. 1 column efflux,
The adsorption rate that rhenium is obtained by the concentration of rhenium in No. 3 column effluxes of measurement is 99.13%；Spent acid flows into No. 4 columns from No. 2 columns simultaneously
Outflow, to No. 2 column adsorption saturations, No. 1 column desorption is finished, and after No. 1 column is come No. 4 columns, spent acid flows into No. 1 column from No. 3 columns
Outflow, and so on；Desorption is carried out to the resin in No. 1 column method particularly includes: first clean resin with deionized water, then lead to
Enter the sodium hydroxide solution desorption of 120L mass fraction 30%, sodium hydroxide solution flow velocity is 0.2BV/h, obtains rhenium in stripping liquid
Concentration is 3271mg/L, compared with 507 times of rhenium concentration enrichment in spent acid；Stripping liquid is placed in vacuum evaporation apparatus and is evaporated to 25L, heat
KOH additional amount is 128g under molten state, is placed in freezer and crystallizes, obtained white crystal is potassium perrhenate, and purity is
99.99%；Filtrate returns in spent acid and re-starts absorption；
4) remaining resin column operation is same as above, in the rate of recovery and purity and step 3) of potassium perrhenate quite.
Embodiment 5
The present embodiment compound amido ethylene system weak-base anion-exchange resin is made by following preparation method: will be gathered
Styrene chlorine ball extracts 10h, 40 DEG C of drying, the matter of polystyrene chlorine ball and dehydrated alcohol with dehydrated alcohol in Soxhlet extractor
Polystyrene chlorine ball after drying is swollen 10 hours in N-Methyl pyrrolidone, then slowly by amount at room temperature than being 1:4
The mixture of dicyclohexyl amine, pyridine, N-methylcyclohexylamine is added, after reacting 6 hours at room temperature, continues after being to slowly warm up to 40 DEG C
Reaction 18 hours, drains mother liquor, isolated resin after reaction；The quality of polystyrene chlorine ball and N-Methyl pyrrolidone
Than for 1:4, polystyrene chlorine ball and dicyclohexyl amine, pyridine, N-methylcyclohexylamine mass ratio be 3:8:4:6.
The method of the present embodiment high efficiente callback rhenium from Copper making spent acid, comprising the following steps:
1) the above-mentioned compound amido ethylene system weak-base anion-exchange resin of 140L is respectively charged into 4 radical ion exchange columns
(every pillar is packed into 35L resin), and be connected in series, resin first is cleaned with deionized water, then passes to 980L concentration 30%
NaCl solution makes the abundant pre-swollen of resin, then is passed through the H of 840L concentration 30%2SO4Solution converts resin, spare；
2) Copper making spent acid is taken to carry out constituent analysis, it is 6.45mg/L, As that measure S concentration in spent acid, which be 87g/L, Re concentration,
Concentration is that 956mg/L, F concentration are 3.14g/L, and spent acid is squeezed into Gore filter with acid-proof pump, to remove in spent acid partial size 1
μm or more solid particulate matter, wherein the aperture of filter bag is at 1 μm or more；
3) 4 radical ion exchange columns are used in series, last root is spare, by filtered spent acid constant flow pump with 20BV/h's
Flow velocity imports No. 1 ion exchange column, flows out from No. 3 ion exchange columns, in ion exchange process after 4h detection absorption in liquid
The concentration of rhenium, after absorption carries out 96h, rhenium concentration stops absorption, to No. 1 column close to the rhenium concentration in spent acid in No. 1 column efflux
It is desorbed, the adsorption rate that rhenium is obtained by the concentration of rhenium in No. 3 column effluxes of measurement is 92.91%；Spent acid is from No. 2 columns simultaneously
The outflow of No. 4 columns is flowed into, to No. 2 column adsorption saturations, No. 1 column desorption is finished, and after No. 1 column is come No. 4 columns, spent acid is from No. 3 columns
No. 1 column outflow is flowed into, and so on；Desorption is carried out to the resin in No. 1 column method particularly includes: first cleaned with deionized water
Resin, then it is passed through the sodium hydroxide solution desorption of 120L mass fraction 5%, sodium hydroxide solution flow velocity is 10BV/h, is solved
Rhenium concentration is 1808mg/L in imbibition, compared with 280 times of rhenium concentration enrichment in spent acid；Stripping liquid is placed in vacuum evaporation apparatus and is evaporated
To 25L, KOH additional amount is 71g under thermosol state, is placed in freezer and crystallizes, obtained white crystal is potassium perrhenate, purity
It is 99.32%；Filtrate returns in spent acid and re-starts absorption；
4) remaining resin column operation is same as above, in the rate of recovery and purity and step 3) of potassium perrhenate quite.
Comparative example
The method for recycling rhenium in this comparative example from Copper making spent acid, steps are as follows:
1) 140L strong-base anion-exchange resin 201 × 7 is respectively charged into 4 radical ion exchange columns (every pillar dress
Enter 35L resin), and be connected in series, resin first is cleaned with deionized water, the NaCl solution for then passing to 700L concentration 5% makes to set
Rouge is sufficiently swollen, then is passed through the H of 560L concentration 5%2SO4Solution converts resin, spare；
2) Copper making spent acid is taken to carry out constituent analysis, it is 5.83mg/L, As that measure S concentration in spent acid, which be 98g/L, Re concentration,
Concentration is that 827mg/L, F concentration are 2.82g/L, and spent acid is squeezed into Gore filter with acid-proof pump, to remove in spent acid partial size 1
μm or more solid particulate matter, wherein the aperture of filter bag is at 1 μm or more；
3) 4 radical ion exchange columns are used in series, last root is spare, by filtered spent acid constant flow pump with 7BV/h's
Flow velocity imports No. 1 ion exchange column, flows out from No. 3 columns, detects the concentration of rhenium in liquid after absorption in ion exchange process every 4h,
After absorption carries out 128h, rhenium concentration stops absorption, solves to No. 1 column close to the rhenium concentration in spent acid in No. 1 column efflux
It inhales, the adsorption rate that rhenium is obtained by the concentration of rhenium in No. 3 column effluxes of measurement is 89.23%；Spent acid flows into 4 from No. 2 columns simultaneously
The outflow of number column, to No. 2 column adsorption saturations, No. 1 column desorption is finished, and after No. 1 column is come No. 4 columns, spent acid flows into 1 from No. 3 columns
The outflow of number column, and so on；Desorption is carried out to the resin in No. 1 column method particularly includes: resin first is cleaned with deionized water,
It is passed through the ammonium thiocyanate solution desorption of 140L concentration 10% again, desorption flow velocity is 1.5BV/h, and obtaining rhenium concentration in stripping liquid is
985mg/L, compared with 169 times of rhenium concentration enrichment in spent acid；Stripping liquid is placed in vacuum evaporation apparatus and is evaporated to 14L, is placed in freezer
Middle crystallization, obtained white crystal are ammonium perrhenate, purity 90.85%, and filtrate returns in spent acid and re-starts absorption；
4) remaining resin column operation is same as above.
Claims (9)
1. a kind of method for recycling rhenium from Copper making spent acid using compound amido ethylene system's weak-base anion-exchange resin,
It is characterized in that, comprising the following steps: 1) Copper making spent acid is flowed through and be filled with compound amido ethylene system's weakly-basic anion friendship
Change the ion exchange column absorption of resin；2) it is desorbed with sodium hydroxide solution, collects stripping liquid, stripping liquid obtains high rhenium through evaporative crystallization
Sour potassium；Compound amido ethylene system weak-base anion-exchange resin is made by method comprising the following steps: by polyphenyl second
Alkene chlorine ball is swollen 4 ~ 10h in organic solvent, is then slowly added into the mixture of dicyclohexyl amine, pyridine, N-methylcyclohexylamine, room
After 1 ~ 6h of the lower reaction of temperature, be warming up to 40 ~ 90 DEG C of 6 ~ 18h of reaction, be filtered by vacuum later to get；The polystyrene chlorine ball, two rings
The mass ratio of hexylamine, pyridine and N-methylcyclohexylamine is 3:3 ~ 9:1 ~ 4:2 ~ 6.
2. the method for rhenium is recycled from Copper making spent acid as described in claim 1, which is characterized in that the organic solvent is N,
Dinethylformamide, dimethyl sulfoxide, any one in N-Methyl pyrrolidone.
3. the method for rhenium is recycled from Copper making spent acid as described in claim 1, which is characterized in that the polystyrene chlorine ball
Mass ratio with organic solvent is 1:2 ~ 5.
4. the method for rhenium is recycled from Copper making spent acid as described in claim 1, which is characterized in that the compound amido ethylene
It is before weak-base anion-exchange resin uses through pre-swollen processing and conversion processing.
5. the method for rhenium is recycled from Copper making spent acid as claimed in claim 4, which is characterized in that the pre-swollen processing is adopted
The NaCl solution for being 1% ~ 30% with mass fraction；The conversion processing use mass fraction for 1% ~ 30% sulfuric acid solution.
6. the method for rhenium is recycled from Copper making spent acid as claimed in claim 5, which is characterized in that the NaCl solution, sulphur
The volume of acid solution is 1 ~ 20 times of the anion exchange resin volume.
7. the method for rhenium is recycled from Copper making spent acid as described in claim 1, which is characterized in that the stream of spent acid in step 1)
Speed is 2 ~ 20BV/h.
8. the method for rhenium is recycled from Copper making spent acid as described in claim 1, which is characterized in that sodium hydroxide in step 2
The mass fraction of solution is 5% ~ 30%.
9. the method for rhenium is recycled from Copper making spent acid as described in claim 1, which is characterized in that sodium hydroxide in step 2
The flow velocity of solution is 1 ~ 20BV/h；The volume of sodium hydroxide solution used is compound amido ethylene system's weakly-basic anion exchange tree
0.5 ~ 10 times of rouge volume.
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| CN107857408B (en) * | 2017-12-08 | 2023-05-19 | 暨南大学 | Purifying device and treatment method for PPCPs in drinking water source |
| CN108611496A (en) * | 2018-06-30 | 2018-10-02 | 王胜利 | A method of extracting rhenium from Copper making waste acid |
| CN111413288B (en) * | 2020-03-31 | 2023-06-30 | 安徽工业大学 | Accurate detection method for rhenium in copper smelting multielement mixed waste acid |
| CN114259996B (en) * | 2021-12-06 | 2024-03-19 | 洛阳双罗铼材料科技有限公司 | Spherical rhenium directional adsorbent and application method thereof |
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| CN104945550A (en) * | 2015-06-18 | 2015-09-30 | 东南大学 | Dicyclohexylamine modified ion exchange resin, and preparation method and application of ion exchange resin |
| CN105384195B (en) * | 2015-12-11 | 2017-03-29 | 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 |
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