CN107226880A - 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
- Publication number
- CN107226880A CN107226880A CN201710434010.XA CN201710434010A CN107226880A CN 107226880 A CN107226880 A CN 107226880A CN 201710434010 A CN201710434010 A CN 201710434010A CN 107226880 A CN107226880 A CN 107226880A
- Authority
- CN
- China
- Prior art keywords
- rhenium
- spent acid
- exchange resin
- concentration
- weak
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treatment Of Water By Ion Exchange (AREA)
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
Reclaimed the present invention relates to a kind of compound amido ethene system weak-base anion-exchange resin and from Copper making spent acid
The method of rhenium, belongs to rhenium metal utilization technology field.
Background technology
Rhenium metal has high-melting-point, high intensity, good plasticity and excellent mechanical stability, is aircraft engine turbine
Indispensable element in blade, therefore with very high value.Rhenium does not have independent mineral deposit in nature, is mainly distributed on
In the molybdenite and chalcopyrite of porphyry Cu-Mo deposit, rhenium-containing concentrate during pyrometallurgical smelting due to rhenium sulfide-oxidation and
Generate volatile Re2O7Into flue gas, flue gas is in acid making system purification process, Re2O7HReO is generated into spent acid4, turn into
Carry the raw material of rhenium.Molybdenum smelts rhenium concentration in spent acid and is generally 50~500mg/L, and rhenium concentration is more by comparison, in Copper making spent acid
It is low, generally 2~10mg/L, while containing the impurity element such as substantial amounts of arsenic, copper, sulphur, fluorine, silicon in Copper making spent acid, impurity from
Sub- concentration is significantly larger than rhenium concentration, and wherein sulphur concentration is close to 100g/L, and arsenic concentration is 2~10g/L.How economical and efficient from copper
Smelt and rhenium is reclaimed in spent acid with very big technical difficulty, therefore rhenium is reclaimed from Copper making spent acid and do not cause enough weights
Depending on making the resource eventually enter into neutralization slag and going out of use, both caused the waste of secondary resource, environment is polluted again.
Application publication number discloses one kind for CN102628110A Chinese invention patent and reclaims rhenium from Copper making spent acid
Method, including pre- decopper(ing) adds thiosulfate in Copper making spent acid, and reaction filters decopper(ing) after terminating, then will be thio
Sulfate is added in the decopper(ing) tail washings obtained after filtering, and reaction is filtrated to get rich rhenium concentrate after terminating.The method is needed first to spent acid
Decopper(ing) processing is carried out, and need to be heated reaction temperature control at 40~100 DEG C, increases cost；Products obtained therefrom is rhenium content simultaneously
3%~20% rich rhenium concentrate, wherein also containing the copper and arsenic more much higher than rhenium content, is made and can sell to rhenium is therefrom reclaimed
The ammonium perrhenate product sold, in addition it is also necessary to complicated leaching and purification process.
Application publication number discloses a kind of from copper blast furnace off-gas washing spent acid for CN102502855A Chinese invention patent
The method that extraction prepares ammonium perrhenate in liquid, is included in spent acid and adds mixed organic solvents, and three stage countercurrent extractions are carried out under normal temperature
Take, coordination washing and pure water then are carried out to rhenium-containing load organic phases, then be stripped with ammoniacal liquor, in rhenium-containing strip liquor
Add sec-octyl alcohol and remove organic phase, after obtained rhenium-containing strip liquor standing 20h to faintly acid, extracted, washed again, instead
Extract and except organic phase operation, finally give the secondary rhenium-containing strip liquor of high concentration, finally preparing grade with concentrated frozen crystallization is more than
98% ammonium perrhenate product.The technological process is complicated, it is necessary to extracted, washed twice respectively, is stripped, except organic phase behaviour
Make；Extractant used is volatile, toxic, and new waste water and waste liquid is generated in the process, is unfavorable for environmental protection.
Application publication number discloses one kind for CN103773963A Chinese invention patent and reclaims rhenium from Copper making spent acid
Method, including by steam-coil-heater after Copper making spent acid is once filtered, then successively add flocculant, thiosulfate
Reacted, eventually pass secondary filter, obtain filter residue for copper rhenium sediment.The technological process is simple, and the rate of recovery of rhenium is reachable
To more than 98%, but resulting 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%, to rhenium is made into ammonium perrhenate product, is still needed to
Want complicated separating-purifying process.
Application publication number is efficiently returned in disclosing a kind of smelting spent acid from molybdenum for CN105384195A Chinese invention patent
The method for receiving rhenium, including filtering, the friendship equipped with compound amido ethene system weak-base anion-exchange resin is passed directly into by spent acid
Change post to be adsorbed, then solution with ammonia is inhaled, and evaporative crystallization prepares ammonium perrhenate product.But, compared with molybdenum smelts spent acid, copper
Smelt rhenium concentration lower (2~10mg/L), impurity ion content in spent acid higher, therefore, reclaimed in the above-mentioned smelting spent acid from molybdenum
The method of rhenium is not suitable for Copper making spent acid.
In summary, a kind of technique of exploitation is simple, cost is low, gained perrhenate product purity is high from Copper making spent acid
The middle method for reclaiming rhenium is extremely urgent.
The content of the invention
It is an object of the invention to provide a kind of compound amido ethene system weak-base anion-exchange resin, the resin is to copper
The rhenium smelted in spent acid has good adsorption effect.
Second purpose of the invention is that providing a kind of exchanged using above-mentioned compound amido ethene system weakly-basic anion is set
The method that fat reclaims rhenium from Copper making spent acid, to solve to reclaim rhenium cost height, technique from Copper making spent acid in the prior art
The low technical problem of complicated, gained rhenium-containing product purity.
To achieve the above object, the technical scheme is that：
A kind of compound amido ethene system weak-base anion-exchange resin, is made by the method comprised the following steps：Will be poly-
Styrene chlorine ball is swelled 4~10h in organic solvent, is then slowly added into the mixing of dicyclohexyl amine, pyridine, N-methylcyclohexylamine
Thing, reacts after 1~6h at room temperature, is warming up to 40~90 DEG C of 6~18h of reaction, is filtered by vacuum, produces afterwards；The polystyrene
Chlorine ball, dicyclohexyl amine, the mass ratio of pyridine and N-methylcyclohexylamine are 3:3~9:1~4:2~6.
The polystyrene chlorine ball is extracted before being swelled through absolute ethyl alcohol, drying and processing.The extracting is in surname extraction
Carried out in device.The extraction times are 10h.The mass ratio of the polyethylene chlorine ball and absolute ethyl alcohol is 1:3~8.It is described to dry
Dry temperature is 40 DEG C.
Above-mentioned organic solvent is any one in N,N-dimethylformamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE.
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 aqueous phase of styrene monomer and divinylbenzene monomer, gained copolymer
Obtained by chloromethylation.Chlorinity is 18% in the polystyrene chlorine ball, and the degree of cross linking is 6%.It is of the invention used
The polystyrene chlorine ball degree of cross linking is low, improves the rate of adsorption of the rhenium on resin so that spent acid can be inhaled under higher flow velocity
It is attached.
The polystyrene chlorine ball is purchased from Zhengguang Resin Co., Ltd..
Above-mentioned compound amido ethene system weak-base anion-exchange resin is that milky is spherical, and 700~1400 μm of granularity is wet
Degree 40%~45%, 600~680g/L of wet density.
It is a kind of that rhenium is reclaimed from Copper making spent acid using above-mentioned compound amido ethene system weak-base anion-exchange resin
Method, comprises the following steps：1) Copper making spent acid is flowed through and is filled with compound amido ethene system weak-base anion-exchange resin
Ion exchange column is adsorbed；2) desorbed with sodium hydroxide solution, collect stripping liquid, stripping liquid obtains potassium perrhenate through evaporative crystallization.
Step 1) in Copper making spent acid be the flue gas that is produced in pyrogenic process roasting process of copper concentrate through spray, dedusting, cooling
The spent acid flowed out afterwards in spray column.
The composition of the Copper making spent acid includes S, Re, As, F.
Step 1) in Copper making spent acid before adsorption column is flowed through through filtration treatment.
Above-mentioned filtering purpose is to remove solid particulate matter of the particle diameter more than 1 μm in spent acid.Above-mentioned filtering is preferably adopted
Use Gore filter.Wherein the filter sizes of filter bag are more than 1 μm.Above-mentioned Gore filter is purchased from W. L. Gore ＆ Associates, Inc. company.
The compound amido ethene system weak-base anion-exchange resin is handled and conversion processing using preceding through pre-swollen.
Pre-swollen processing use mass fraction for 1%~30% NaCl solution；The conversion processing uses quality
Fraction is 1%~30% sulfuric acid solution.
The NaCl solution, the volume of sulfuric acid solution are 1~20 times of the anion exchange resin volume.Pre-swollen
Processing is that aperture is opened completely in order that the volume of resin expands completely, so as to increase the specific surface area of ion-exchange reactions；Turn
Change processing be in order to by the ionic type carried on resin functionality be converted into spent acid system identical ionic type, so as to keep away
Exempt to introduce other impurities ion.
Step 1) in spent acid flow velocity be 2~20BV/h.
It is above-mentioned be filled with the ion exchange column adsorption saturation of compound amido ethene system weak-base anion-exchange resin after use hydrogen
Sodium hydroxide solution is desorbed.The resin column adsorption saturation when the concentration of rhenium in solution after absorption is equal to the concentration of rhenium in spent acid.
Step 1) in be filled with the ion exchange column of compound amido ethene system weak-base anion-exchange resin and using process
It is middle to set more than four, connect in a series arrangement, last root is standby.Spent acid after filtering 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, first pillar is desorbed, spent acid
From second inflow, from the outflow of 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, now first pillar desorption is finished, and spent acid is flowed into from the 3rd pillar, from first pillar stream
Go out；So circulation.
Step 2) in sodium hydroxide solution mass fraction be 5%~30%.Strippant uses strong electrolyte sodium hydroxide
Solution, effectively raises desorption efficiency.
Step 2) in sodium hydroxide solution flow velocity be 1~20BV/h；The volume of sodium hydroxide solution used is serotonin
0.5~10 times of base ethene system weak-base anion-exchange resin volume.
Step 2) in evaporative crystallization be that stripping liquid is evaporated to 1%~30%, Ran Hou of original volume under vacuum
KOH is added under thermosol state, cooling in freezer is placed in and obtains potassium perrhenate crystal.The evaporation carries out carrying under vacuum
High evaporation efficiency.
The mol ratio of the KOH and rhenium in stripping liquid is 0.5~3:1.
Step 2) in after evaporative crystallization filtering produce potassium perrhenate.Filtrate can return in spent acid and be adsorbed again.
The beneficial effects of the invention are as follows：
The synthesis material of the compound amido ethene system weak-base anion-exchange resin of the present invention is common medicine, cost
It is low, while gained resin has good adsorptivity to rhenium.
The present invention reclaims the side of rhenium using compound amido ethene 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 flow, avoids simultaneously
Loss of the rhenium in N-process；Resin used is particularly virose arsenate ion to foreign ion and not adsorbed substantially,
There is good adsorptive selectivity to rhenium, while also having excellent desorption performance, stripping liquid uses cheap sodium hydroxide
Solution can desorb rhenium completely from resin.
The present invention is reclaimed from Copper making spent acid in the method for rhenium, by the way of ion exchange column is connected, can both be ensured
Resin can be adsorbed completely, and the loss of rhenium in efflux is reduced again, so that the rate of recovery of rhenium is maintained at more than 97%, and be inhaled
Attached spent acid can be directly entered the wastewater treatment working section of smeltery, and new waste water and waste liquid is not produced, 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, improves under vacuum conditions
Evaporation efficiency, while liquid can be realized and recycled after evaporation, makes rhenium not lose substantially in the process, while perrhenic acid is made
Potassium product purity is more than 99.9%.
Brief description of the drawings
Fig. 1 is the process flow diagram that rhenium is reclaimed from Copper making spent acid.
Embodiment
Embodiments of the present invention are described further below in conjunction with the accompanying drawings.
Embodiment 1
The present embodiment is combined amido ethene system weak-base anion-exchange resin, is made by the method comprised the following steps：
By polystyrene chlorine ball in apparatus,Soxhlet's with absolute ethyl alcohol extract 10h, then 40 DEG C drying, polystyrene chlorine ball with it is anhydrous
The mass ratio of ethanol is 1:3；Polystyrene chlorine ball after drying is swelled 5 in N,N-dimethylformamide at room temperature small
When, the mixture of dicyclohexyl amine, pyridine, N-methylcyclohexylamine is then slowly added into, after reacting 2 hours at room temperature, slow heating
Continue to react 8 hours after to 50 DEG C, mother liquor is drained in reaction after terminating, vacuum filtration obtains resin；Wherein polystyrene chlorine ball with
The mass ratio of N,N-dimethylformamide is 1:2, polystyrene chlorine ball and dicyclohexyl amine, pyridine, the quality of N-methylcyclohexylamine
Than for 3:3:1:3.The granularity of compound amido ethene system weak-base anion-exchange resin is 800 μm, humidity obtained by the present embodiment
40%, wet density 620g/L.
The method that the present embodiment reclaims rhenium from Copper making spent acid, as shown in figure 1, comprising the following steps：
1) the above-mentioned compound amido ethene system weak-base anion-exchange resins of 140L are respectively charged into 4 radical ion exchange columns
(every pillar loads 35L resins), and be connected in series, resin first is cleaned with deionized water, 700L concentration 15% is then passed to
NaCl solution makes the abundant pre-swollen of resin, then is passed through the H of 560L concentration 15%2SO4Solution is converted to resin, standby；
2) Copper making spent acid is taken to carry out constituent analysis, it is that 92g/L, Re concentration are 5.74mg/L, As to measure S concentration in spent acid
Concentration is that 896mg/L, F concentration are 2.68g/L, and spent acid is squeezed into Gore filter (being purchased from W. L. Gore ＆ Associates, Inc. company) with acid-proof pump,
To remove solid particulate matter of the particle diameter more than 1 μm in spent acid, wherein the aperture of filter bag is more than 1 μm；
3) 4 radical ion exchange columns are used in series, and last root is standby, by the spent acid constant flow pump after filtering with 7BV/h's
Flow velocity imports No. 1 ion exchange column, every in liquid after 4h detection absorption from No. 3 ion exchange column outflows, ion exchange process
The concentration of rhenium, absorption is carried out after 144h, and rhenium concentration stops absorption, to No. 1 close to the rhenium concentration in spent acid in No. 1 post efflux
Post is desorbed, and the adsorption rate that rhenium is obtained by measuring the concentration of rhenium in No. 3 post effluxes is 98.96%；Then spent acid is from No. 2
Post flows into the outflow of No. 4 posts, treats No. 2 post adsorption saturations, and No. 1 post desorption is finished, and after No. 1 post come into No. 4 posts, spent acid is from No. 3
Post flows into No. 1 post outflow, by that analogy；It is to the specific method that the resin in No. 1 post carries out desorption：It is first clear with deionized water
Resin is washed, then is passed through the sodium hydroxide solution that 100L mass fractions are 15% and is desorbed, 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
14L is evaporated to, KOH additions are 91g under thermosol state, is placed in freezer and crystallizes, obtained white crystal as perrhenic acid
Potassium, purity is 99.94%；Filtrate, which is returned in spent acid, re-starts absorption；
4) remaining resin post adsorption and desorption operation ibid, the rate of recovery and purity and step 3 of potassium perrhenate) in phase
When.
Embodiment 2
The present embodiment is combined amido ethene system weak-base anion-exchange resin, by the preparation method system comprised the following steps
：By polystyrene chlorine ball in apparatus,Soxhlet's with absolute ethyl alcohol extract 10h, 40 DEG C drying, polystyrene chlorine ball with it is anhydrous
The mass ratio of ethanol is 1:5, the polystyrene chlorine ball after drying is swelled 6 hours in dimethyl sulfoxide (DMSO) at room temperature, then
The mixture of dicyclohexyl amine, pyridine, N-methylcyclohexylamine is slowly added to, after reacting 4 hours at room temperature, is to slowly warm up to after 70 DEG C
Continue to react 10 hours, after reaction terminates, vacuum filtration obtains resin；Wherein, the matter of polystyrene chlorine ball and dimethyl sulfoxide (DMSO)
Amount is than being 1:3, the mass ratio of polystyrene chlorine ball and dicyclohexyl amine, pyridine, N-methylcyclohexylamine is 3:6:2:4.The present embodiment
The granularity that gained is combined amido ethene system weak-base anion-exchange resin is 900 μm, humidity 43%, wet density 640g/L.
The method that the present embodiment reclaims rhenium from Copper making spent acid, comprises the following steps：
1) the above-mentioned compound amido ethene system weak-base anion-exchange resins of 140L are respectively charged into 4 radical ion exchange columns
(every pillar loads 35L resins), and be connected in series, resin first is cleaned with deionized water, 700L concentration 10% is then passed to
NaCl solution makes the abundant pre-swollen of resin, then is passed through the H of 700L concentration 10%2SO4Solution is converted to resin, standby；
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 particle diameter in spent acid
The aperture of solid particulate matter more than 1 μm, wherein filter bag is more than 1 μm；
3) 4 radical ion exchange columns are used in series, and last root is standby, by the spent acid constant flow pump after filtering with 8BV/h's
Flow velocity imports No. 1 ion exchange column, from No. 3 post outflows, detects the concentration of rhenium in liquid after absorption in ion exchange process every 4h,
Absorption is carried out after 122h, and rhenium concentration stops absorption, No. 1 post is solved close to the rhenium concentration in spent acid in No. 1 post efflux
Inhale, the adsorption rate that rhenium is obtained by measuring the concentration of rhenium in No. 3 post effluxes is 98.03%；Then spent acid flows into 4 from No. 2 posts
The outflow of number post, treats No. 2 post adsorption saturations, and No. 1 post desorption is finished, and after No. 1 post come into No. 4 posts, spent acid flows into 1 from No. 3 posts
The outflow of number post, by that analogy；It is to the specific method that the resin in No. 1 post carries out desorption：Resin first is cleaned with deionized water,
The sodium hydroxide solution desorption of 90L mass fractions 20% is passed through again, and 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 additions are 63g under thermosol state, are placed in freezer and crystallize, obtained white crystal as potassium perrhenate, and purity is
99.96%；Filtrate returns in spent acid and re-starts absorption；
4) remaining resin post adsorption and desorption operation ibid, the rate of recovery and purity and step 3 of potassium perrhenate) in phase
When.
Embodiment 3
The present embodiment is combined amido ethene system weak-base anion-exchange resin, is made by following preparation method：Will be poly-
Styrene chlorine ball extracts 10h in apparatus,Soxhlet's with absolute ethyl alcohol, and 40 DEG C dry, the matter of polystyrene chlorine ball and absolute ethyl alcohol
Amount is than being 1:8, the polystyrene chlorine ball after drying is swelled 8 hours in 1-METHYLPYRROLIDONE at room temperature, then slowly
Dicyclohexyl amine, pyridine, the mixture of N-methylcyclohexylamine are added, after reacting 6 hours at room temperature, is to slowly warm up to continue after 80 DEG C
Reaction 12 hours, after reaction terminates, vacuum filtration obtains resin；The mass ratio of polystyrene chlorine ball and 1-METHYLPYRROLIDONE is
1:5, the mass ratio of polystyrene chlorine ball and dicyclohexyl amine, pyridine, N-methylcyclohexylamine is 3:8:3:6.It is multiple obtained by the present embodiment
The granularity for closing amido ethene system weak-base anion-exchange resin is 1100 μm, humidity 44%, wet density 660g/L.
The method that the present embodiment reclaims rhenium from Copper making spent acid, comprises the following steps：
1) the above-mentioned compound amido ethene system weak-base anion-exchange resins of 140L are respectively charged into 4 radical ion exchange columns
(every pillar loads 35L resins), and be connected in series, resin first is cleaned with deionized water, 980L concentration 5% is then passed to
NaCl solution makes resin fully be swelled, then is passed through the H of 840L concentration 5%2SO4Solution is converted to resin, standby；
2) Copper making spent acid is taken to carry out constituent analysis, it is that 87g/L, Re concentration are 6.45mg/L, As to measure S concentration in spent acid
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 particle diameter 1
The aperture of solid particulate matter more than μm, wherein filter bag is more than 1 μm；
3) 4 radical ion exchange columns are used in series, and last root is standby, by the spent acid constant flow pump after filtering with 9BV/h's
Flow velocity imports No. 1 ion exchange column, every in liquid after 4h detection absorption from No. 3 ion exchange column outflows, ion exchange process
The concentration of rhenium, absorption is carried out after 96h, and rhenium concentration stops absorption, to No. 1 post close to the rhenium concentration in spent acid in No. 1 post efflux
Desorbed, the adsorption rate that rhenium is obtained by measuring the concentration of rhenium in No. 3 post effluxes is 97.46%；Then spent acid is from No. 2 posts
The outflow of No. 4 posts is flowed into, No. 2 post adsorption saturations are treated, No. 1 post desorption is finished, after No. 1 post come into No. 4 posts, spent acid is from No. 3 posts
No. 1 post outflow is flowed into, by that analogy；It is to the specific method that the resin in No. 1 post carries out desorption：First cleaned with deionized water
Resin, then the sodium hydroxide solution desorption of 120L mass fractions 10% is passed through, 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 evaporated
To 25L, KOH additions are 96g under thermosol state, are placed in freezer and crystallize, and filtrate is returned in stripping liquid, obtained white crystal
As potassium perrhenate, purity is 99.98%；Filtrate returns in spent acid and re-starts absorption；
4) remaining resin post adsorption and desorption operation ibid, the rate of recovery and purity and step 3 of potassium perrhenate) in phase
When.
Embodiment 4
The present embodiment is combined amido ethene system weak-base anion-exchange resin, by the preparation method system comprised the following steps
：By polystyrene chlorine ball in apparatus,Soxhlet's with absolute ethyl alcohol extract 10h, 40 DEG C drying, polystyrene chlorine ball with it is anhydrous
The mass ratio of ethanol is 1:8, the polystyrene chlorine ball after drying is swelled 4 hours in 1-METHYLPYRROLIDONE at room temperature,
The mixture of dicyclohexyl amine, pyridine, N-methylcyclohexylamine is then slowly added into, after reacting 1 hour at room temperature, 90 are to slowly warm up to
Continue to react 6 hours after DEG C, reaction is filtered by vacuum after terminating, and obtains resin；Polystyrene chlorine ball and 1-METHYLPYRROLIDONE
Mass ratio is 1:3, the mass ratio of polystyrene chlorine ball and dicyclohexyl amine, pyridine, N-methylcyclohexylamine is 3:9:4:2.
The method that the present embodiment reclaims rhenium from Copper making spent acid, comprises the following steps：
1) the above-mentioned compound amido ethene system weak-base anion-exchange resins of 140L are respectively charged into 4 radical ion exchange columns
(every pillar loads 35L resins), and be connected in series, resin first is cleaned with deionized water, 980L concentration 1% is then passed to
NaCl solution makes the abundant pre-swollen of resin, then is passed through the H2SO4 solution of 840L concentration 1% resin is converted, standby；
2) Copper making spent acid is taken to carry out constituent analysis, it is that 87g/L, Re concentration are 6.45mg/L, As to measure S concentration in spent acid
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 particle diameter 1
The aperture of solid particulate matter more than μm, wherein filter bag is more than 1 μm；
3) 4 radical ion exchange columns are used in series, and last root is standby, by the spent acid constant flow pump after filtering with 3BV/h's
Flow velocity imports No. 1 ion exchange column, from No. 3 post outflows, detects the concentration of rhenium in liquid after absorption in ion exchange process every 4h,
Absorption is carried out after 96h, and rhenium concentration stops absorption, No. 1 post is desorbed close to the rhenium concentration in spent acid in No. 1 post efflux,
The adsorption rate that rhenium is obtained by measuring the concentration of rhenium in No. 3 post effluxes is 99.13%；Spent acid flows into No. 4 posts from No. 2 posts simultaneously
Outflow, treats No. 2 post adsorption saturations, and No. 1 post desorption is finished, and after No. 1 post come into No. 4 posts, spent acid flows into No. 1 posts from No. 3 posts
Outflow, by that analogy；It is to the specific method that the resin in No. 1 post carries out desorption：Resin is first cleaned with deionized water, then is led to
Enter the sodium hydroxide solution desorption of 120L mass fractions 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 additions are 128g under molten state, are placed in freezer and crystallize, obtained white crystal as potassium perrhenate, and purity is
99.99%；Filtrate returns in spent acid and re-starts absorption；
4) remaining resin column operation ibid, the rate of recovery and purity of potassium perrhenate and step 3) in quite.
Embodiment 5
The present embodiment is combined amido ethene system weak-base anion-exchange resin, is made by following preparation method：Will be poly-
Styrene chlorine ball extracts 10h in apparatus,Soxhlet's with absolute ethyl alcohol, and 40 DEG C dry, the matter of polystyrene chlorine ball and absolute ethyl alcohol
Amount is than being 1:4, the polystyrene chlorine ball after drying is swelled 10 hours in 1-METHYLPYRROLIDONE at room temperature, then slowly
Dicyclohexyl amine, pyridine, the mixture of N-methylcyclohexylamine are added, after reacting 6 hours at room temperature, is to slowly warm up to continue after 40 DEG C
Reaction 18 hours, reaction drains mother liquor, isolated resin after terminating；The quality of polystyrene chlorine ball and 1-METHYLPYRROLIDONE
Than for 1:4, the mass ratio of polystyrene chlorine ball and dicyclohexyl amine, pyridine, N-methylcyclohexylamine is 3:8:4:6.
The method of the present embodiment high efficiente callback rhenium from Copper making spent acid, comprises the following steps：
1) the above-mentioned compound amido ethene system weak-base anion-exchange resins of 140L are respectively charged into 4 radical ion exchange columns
(every pillar loads 35L resins), and be connected in series, resin first is cleaned with deionized water, 980L concentration 30% is then passed to
NaCl solution makes the abundant pre-swollen of resin, then is passed through the H of 840L concentration 30%2SO4Solution is converted to resin, standby；
2) Copper making spent acid is taken to carry out constituent analysis, it is that 87g/L, Re concentration are 6.45mg/L, As to measure S concentration in spent acid
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 particle diameter 1
The aperture of solid particulate matter more than μm, wherein filter bag is more than 1 μm；
3) 4 radical ion exchange columns are used in series, and last root is standby, by the spent acid constant flow pump after filtering with 20BV/h's
Flow velocity imports No. 1 ion exchange column, every in liquid after 4h detection absorption from No. 3 ion exchange column outflows, ion exchange process
The concentration of rhenium, absorption is carried out after 96h, and rhenium concentration stops absorption, to No. 1 post close to the rhenium concentration in spent acid in No. 1 post efflux
Desorbed, the adsorption rate that rhenium is obtained by measuring the concentration of rhenium in No. 3 post effluxes is 92.91%；Spent acid is from No. 2 posts simultaneously
The outflow of No. 4 posts is flowed into, No. 2 post adsorption saturations are treated, No. 1 post desorption is finished, after No. 1 post come into No. 4 posts, spent acid is from No. 3 posts
No. 1 post outflow is flowed into, by that analogy；It is to the specific method that the resin in No. 1 post carries out desorption：First cleaned with deionized water
Resin, then the sodium hydroxide solution desorption of 120L mass fractions 5% is passed through, 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 evaporated
To 25L, KOH additions are 71g under thermosol state, are placed in freezer and crystallize, obtained white crystal as potassium perrhenate, purity
For 99.32%；Filtrate returns in spent acid and re-starts absorption；
4) remaining resin column operation ibid, the rate of recovery and purity of potassium perrhenate and step 3) in quite.
Comparative example
The method for reclaiming rhenium in this comparative example from Copper making spent acid, step is as follows：
1) 140L strong-base anion-exchange resins 201 × 7 are respectively charged into 4 radical ion exchange columns (every pillar dress
Enter 35L resins), and be connected in series, resin first is cleaned with deionized water, then passing to the NaCl solution of 700L concentration 5% makes tree
Fat is fully swelled, then is passed through the H of 560L concentration 5%2SO4Solution is converted to resin, standby；
2) Copper making spent acid is taken to carry out constituent analysis, it is that 98g/L, Re concentration are 5.83mg/L, As to measure S concentration in spent acid
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 particle diameter 1
The aperture of solid particulate matter more than μm, wherein filter bag is more than 1 μm；
3) 4 radical ion exchange columns are used in series, and last root is standby, by the spent acid constant flow pump after filtering with 7BV/h's
Flow velocity imports No. 1 ion exchange column, from No. 3 post outflows, detects the concentration of rhenium in liquid after absorption in ion exchange process every 4h,
Absorption is carried out after 128h, and rhenium concentration stops absorption, No. 1 post is solved close to the rhenium concentration in spent acid in No. 1 post efflux
Inhale, the adsorption rate that rhenium is obtained by measuring the concentration of rhenium in No. 3 post effluxes is 89.23%；Spent acid flows into 4 from No. 2 posts simultaneously
The outflow of number post, treats No. 2 post adsorption saturations, and No. 1 post desorption is finished, and after No. 1 post come into No. 4 posts, spent acid flows into 1 from No. 3 posts
The outflow of number post, by that analogy；It is to the specific method that the resin in No. 1 post carries out desorption：Resin first is cleaned with deionized water,
The ammonium thiocyanate solution desorption of 140L concentration 10% is passed through again, and 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, freezer is placed in
Middle crystallization, obtained white crystal as ammonium perrhenate, purity is 90.85%, and filtrate returns in spent acid and re-starts absorption；
4) remaining resin column operation is ibid.
Claims (10)
1. a kind of compound amido ethene system weak-base anion-exchange resin, it is characterised in that the method by comprising the following steps
It is made：Polystyrene chlorine ball is swelled 4~10h in organic solvent, dicyclohexyl amine, pyridine, N- methyl rings is then slowly added into
The mixture of hexylamine, reacts after 1~6h at room temperature, is warming up to 40~90 DEG C of 6~18h of reaction, is filtered by vacuum, produces afterwards；Institute
The mass ratio for stating polystyrene chlorine ball, dicyclohexyl amine, pyridine and N-methylcyclohexylamine is 3:3~9:1~4:2~6.
2. amido ethene system weak-base anion-exchange resin is combined as claimed in claim 1, it is characterised in that described organic
Solvent is any one in N,N-dimethylformamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE.
3. amido ethene system weak-base anion-exchange resin is combined as claimed in claim 1, it is characterised in that the polyphenyl
The mass ratio of ethene chlorine ball and organic solvent is 1:2~5.
4. one kind is using the amido ethene system's weak-base anion-exchange resin as claimed in claim 1 that is combined from Copper making spent acid
The middle method for reclaiming rhenium, it is characterised in that comprise the following steps：1) Copper making spent acid is flowed through and is filled with the compound amido ethene
It is the ion exchange column absorption of weak-base anion-exchange resin；2) desorbed with sodium hydroxide solution, collect stripping liquid, stripping liquid
Potassium perrhenate is obtained through evaporative crystallization.
5. the method for rhenium is reclaimed from Copper making spent acid as claimed in claim 4, it is characterised in that the compound amido ethene
It is that weak-base anion-exchange resin is handled and conversion processing using preceding through pre-swollen.
6. the method for rhenium is reclaimed from Copper making spent acid as claimed in claim 5, it is characterised in that the pre-swollen processing is adopted
With the NaCl solution that mass fraction is 1%~30%；The conversion processing uses mass fraction molten for 1%~30% sulfuric acid
Liquid.
7. the method for rhenium is reclaimed from Copper making spent acid as claimed in claim 6, it is characterised in that the NaCl solution, sulphur
The volume of acid solution is 1~20 times of the anion exchange resin volume.
8. as claimed in claim 4 from Copper making spent acid reclaim rhenium method, it is characterised in that step 1) in spent acid stream
Speed is 2~20BV/h.
9. as claimed in claim 4 from Copper making spent acid reclaim rhenium method, it is characterised in that step 2) in sodium hydroxide
The mass fraction of solution is 5%~30%.
10. as claimed in claim 4 from Copper making spent acid reclaim rhenium method, it is characterised in that step 2) in hydroxide
The flow velocity of sodium solution is 1~20BV/h；The volume of sodium hydroxide solution used is that compound amido ethene system weakly-basic anion is handed over
Change resin volume 0.5~10 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710434010.XA CN107226880B (en) | 2017-06-09 | 2017-06-09 | Composite amino ethylene series weak-alkaline anion exchange resin and method for recovering rhenium from copper smelting waste acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710434010.XA CN107226880B (en) | 2017-06-09 | 2017-06-09 | Composite amino ethylene series weak-alkaline anion exchange resin and method for recovering rhenium from copper smelting waste acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107226880A true CN107226880A (en) | 2017-10-03 |
| CN107226880B CN107226880B (en) | 2019-04-12 |
Family
ID=59935946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710434010.XA Active CN107226880B (en) | 2017-06-09 | 2017-06-09 | Composite amino ethylene series weak-alkaline anion exchange resin and method for recovering rhenium from copper smelting waste acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107226880B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107857408A (en) * | 2017-12-08 | 2018-03-30 | 暨南大学 | PPCPs purifier and processing method in a kind of drinking water source |
| CN107899621A (en) * | 2017-10-26 | 2018-04-13 | 东南大学 | A kind of aromatic sulphonic acid selective ion exchange resin and preparation method and application |
| CN108611496A (en) * | 2018-06-30 | 2018-10-02 | 王胜利 | A method of extracting rhenium from Copper making waste acid |
| CN111413288A (en) * | 2020-03-31 | 2020-07-14 | 安徽工业大学 | Accurate detection method for rhenium in copper smelting multi-element mixed waste acid |
| CN114259996A (en) * | 2021-12-06 | 2022-04-01 | 洛阳双罗铼材料科技有限公司 | Spherical rhenium directional adsorbent and application method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788599A (en) * | 2015-03-27 | 2015-07-22 | 徐州浩通新材料科技股份有限公司 | Preparation method for macroporous weak-base anion exchange resin |
| 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 |
| CN105384195A (en) * | 2015-12-11 | 2016-03-09 | 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 |
-
2017
- 2017-06-09 CN CN201710434010.XA patent/CN107226880B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788599A (en) * | 2015-03-27 | 2015-07-22 | 徐州浩通新材料科技股份有限公司 | Preparation method for macroporous weak-base anion exchange resin |
| 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 |
| CN105384195A (en) * | 2015-12-11 | 2016-03-09 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| 陈家镛等: "《湿法冶金手册》", 30 September 2005, 冶金工业出版社 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107899621A (en) * | 2017-10-26 | 2018-04-13 | 东南大学 | A kind of aromatic sulphonic acid selective ion exchange resin and preparation method and application |
| CN107857408A (en) * | 2017-12-08 | 2018-03-30 | 暨南大学 | PPCPs purifier and processing method in a kind of drinking water source |
| 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 |
| CN111413288A (en) * | 2020-03-31 | 2020-07-14 | 安徽工业大学 | Accurate detection method for rhenium in copper smelting multi-element mixed 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 |
| CN114259996A (en) * | 2021-12-06 | 2022-04-01 | 洛阳双罗铼材料科技有限公司 | Spherical rhenium directional adsorbent and application method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107226880B (en) | 2019-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107226880B (en) | Composite amino ethylene series weak-alkaline anion exchange resin and method for recovering rhenium from copper smelting waste acid | |
| CN105384195B (en) | Method for recovering rhenium from molybdenum smelting waste acid | |
| CN102649998B (en) | Method for separating and enriching copper, cadmium and zinc in copper and cadmium sediment | |
| CN105293584B (en) | A kind of method of purification of sulphuric acids manganese solution | |
| CN108342583A (en) | A method of recycling rhenium and molybdenum from calcining molybdenum ore concentrate collected ash | |
| CN106148689B (en) | The method that oxygen presses acidleach efficiently concentrating gold and platinum group metal concentrate | |
| CN105274348A (en) | Method for extracting rhenium from copper smelting flue gas wet dust collecting liquid | |
| CN109881007A (en) | A method of the comprehensive utilization of acid water containing arsenic | |
| CN102701263A (en) | Method for preparing copper sulfate in mode that stanniferous copper slag is leached in selective mode and free of evaporation | |
| CN104108740B (en) | A kind of novel method of selectivity production high-quality copper sulfate from copper-bearing waste material | |
| CN105714121B (en) | A kind of method that rhenium and bismuth are reclaimed from acid waste liquid | |
| CN108611496A (en) | A method of extracting rhenium from Copper making waste acid | |
| CN103159261A (en) | Method using sodium molybdate solution to prepare ammonium molybdate | |
| CN107519948A (en) | Composite amino weakly-alkaline anion exchange resin and method for recovering rhenium from arsenic sulfide slag leachate | |
| CN108517538B (en) | The method of waste solution of copper electrolysis synthetical recovery processing | |
| CN107354300B (en) | A method of the enriching rhenium from Copper making spent acid | |
| CN104148022B (en) | Amine-modified persimmon tannin adsorbent, and preparation method and application thereof | |
| CN107555469B (en) | A kind of technique preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia | |
| CN110846510B (en) | Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid | |
| CN105983707B (en) | A method of high-purity rhenium powder is prepared from rhenium-containing high arsenic-and copper-bearing sulfide | |
| CN103966439B (en) | In a kind of copper and sulfide tailings, the leachate separating-purifying of metal rubidium resource reclaim processes technique | |
| CN107574305A (en) | A kind of high concn. arsenic and lead matte Recovering Copper and sulphur technique | |
| CN104745837B (en) | Recovery process of palladium in copper-nickel alloy | |
| CN104831062A (en) | A method of extracting valuable elements by utilization of sulfur concentrate | |
| US8361192B2 (en) | Methods and systems for recovering rhenium from a copper leach |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |