CN111413288A - Accurate detection method for rhenium in copper smelting multi-element mixed waste acid - Google Patents
Accurate detection method for rhenium in copper smelting multi-element mixed waste acid Download PDFInfo
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Abstract
The invention discloses an accurate detection method for rhenium in copper smelting multi-element mixed waste acid, and belongs to the field of scattered metal analysis and detection. The method comprises four steps of resin pretreatment, rhenium adsorption in the copper smelting multi-component mixed waste acid, resin-rich rhenium desorption and rhenium content detection, and rhenium is efficiently and selectively transferred from the copper smelting multi-component mixed waste acid by adopting an organic amine type macroporous weak-base anion exchange resin, so that the defects of large influence of impurity ions, serious matrix effect, larger deviation of detection results, poor environmental protection, longer period and the like in the process of analyzing and detecting rhenium in the copper smelting multi-component mixed waste acid in the prior art are effectively overcome, the rapid detection is realized, and the technical support is provided for enrichment and purification of rhenium in the copper smelting multi-component mixed waste acid.
Description
Technical Field
The invention belongs to the field of scattered metal analysis and detection, and particularly relates to a novel method for quickly, simply and accurately detecting scattered metal rhenium in copper smelting multi-component mixed waste acid.
Background
Rhenium is one of seven important rare metals, and the abundance in the earth crust is only 10-8% rhenium has a melting point of 3170 ℃ second only to tungsten, a boiling point of up to 5900 ℃ and a density of up to 21.02g/cm3. The high melting point, the high corrosion resistance and the extremely strong plasticity of rhenium enable the rhenium to form an alloy material with excellent performance and a rhenium effect with various transition metals, and the rhenium alloy material has special and key applications in the aspects of aeroengines, nuclear reactor alloys, missile high-temperature components, special crucibles, over-temperature materials and the like; rhenium has an unsaturated 5d electron layer, easily gives 5d electrons and has a larger lattice parameter, so that rhenium and various compounds thereof have special catalytic activity and have irreplaceable application in petroleum reformation and lead-free gasoline production.
Rhenium resources have a common resource of rare metals and are difficult to form into independent deposits of exploitation value. Due to the ReS2And MoS2Have the same flaky crystal structure, often enter molybdenite crystal lattices in a similar manner and accompany molybdenum; meanwhile, rhenium and copper have similar ionic radii and very similar chemical properties, and often enter chalcocite in a similar manner. Therefore, molybdenum concentrate, copper concentrate and copper-molybdenum concentrate become the main raw materials for recovering rhenium. In the copper pyrometallurgy process, most rhenium in the concentrate is volatilized after being oxidized and enters SO2In the purification of washing waste water, the waste water is called waste acid or waste acid in industry, and contains various anions, which can be called multi-element mixed waste acid, so that the copper smelting waste acid becomes the main raw material for recovering rhenium.
China is the largest global copper smelting production base, the copper yield is always stable in the world for many years, 978 ten thousand tons of refined copper are obtained in 2019, and about 80% of the refined copper is produced by a pyrogenic process. Statistics show that about 1 ton of smelting waste acid is generated by smelting 1 ton of copper by a pyrogenic process, the rhenium content in the copper smelting waste acid is several to hundreds ppm, the annual waste acid produced by copper smelting is about 780 ten thousand tons, and the rhenium content in the annual waste acid produced by copper smelting can reach about 78 tons according to the estimation that the rhenium content is 10 ppm. Therefore, the copper smelting multi-element mixed waste acid is a great raw material source of rhenium. The method has very important significance in the links of resource general survey, enrichment process research, industrial test, production control and the like of rhenium in the multi-element mixed waste acid in copper smelting.
At present, the detection methods of rhenium in the copper smelting multi-component mixed waste acid are more, and the methods mainly comprise a spectrophotometry method, an ICP-AES method, an ICP-MS method, an atomic absorption method, an electrochemical analysis method and the like. The instrument has the advantages of low cost, simple and convenient operation, good selectivity and the like, and always occupies a main position in the field of rhenium detection; with the popularization of precision instruments ICP-AES and ICP-MS in most large enterprises, because the sensitivity, precision and accuracy of the instruments are high, samples are simple to process and can detect various elements simultaneously, the instruments become important detection means step by step, and other detection methods are relatively less in application due to the limitation of various factors. Because various low-melting-point components enter waste acid through flue gas in the copper pyrometallurgy process, the copper smelting waste acid components are very complex, and the waste acid components also contain various impurities such as copper, lead, zinc, mercury, selenium, fluorine, chlorine, arsenic, rhenium, thallium and the like under high sulfuric acid concentration, so that stronger matrix effect and spectral interference can be generated in the instrument analysis process, and the detection result deviation is larger or the sample cannot be detected.
Through searching, relevant patent is published about analyzing and detecting rhenium in solution by spectrophotometry. For example, the method uses the holy leaf (Chinese patent application number is 201610191311.X) to separate impurities from leachate, solution after molybdenum precipitation, strip liquor and crystal mother liquor by two extraction processes of trichloromethane and ethyl acetate, and then detects rhenium in the organic phase; huhui (Chinese patent application No. 201711143815.5) extracts and removes impurities from a multi-impurity liquid sample of copper, lead, molybdenum and technetium smeltery by adopting organic matters such as ketone, ester, ether and the like, and the organic phase detects rhenium by an ultraviolet-spectrophotometer; however, the method has more detection steps and longer flow, and uses more highly toxic organic reagents in the process, thus having great harm to human body and environment.
Patents or literature relating to the pretreatment for separation of impurity ions in an acidic solution thereof have also been disclosed. Such as Duxiahui (Chinese patent application No. 201410842957.0) and Liuwei Li (Chinese molybdenum industry),2015, 39(6): 48-50) adding Ca (OH) into the sample aiming at the low-rhenium high sulfate radical waste liquid2Removing sulfate ion and iron ion, adding Na2CO3Calcium ions in the filtrate are removed, the filtrate is used for detecting rhenium by adopting a spectrophotometry after impurity ions are eliminated, but the calcium sulfate precipitation formed in the process is large in amount, the water content of a filter cake is high (generally more than 40%), and rhenium is easily adsorbed by filtering the filter cake twice, so that loss is caused. For another example, Wang Tong Min (Gansu metallurgy, 2017, 39 (6): 56-59, 63) uses acetone to extract rhenium after pretreating the contaminated acid liquid, and uses ICP-AES to detect the rhenium content; the Qiu Sheng (chemistry and chemical engineering, 2019, 159 and 160) detects the rhenium content by directly adopting ICP-AES (inductively coupled plasma-atomic emission spectrometry) aiming at a primary kinetic wave sample through pretreatment and impurity ion masking, but the pretreatment operation in the process is complex, the rhenium content of a target element is low, the content of fluorine ions in waste acid is high, the instrument is greatly corroded, and the instrument is not suitable for being directly detected.
In summary, because of the multiple types of impurities, the large difference of the content and the low content in the copper smelting multi-element mixed waste acid and the low content of the target element rhenium, a feasible result is difficult to obtain by direct instrument detection, and the existing impurity removal pretreatment method has the defects of complex process operation, large toxicity of part of reagents and the like. Therefore, the method has the advantages of low cost, simple and convenient detection, high accuracy and good precision, and has great significance for recovering rhenium from the copper smelting waste acid.
Disclosure of Invention
1. Problems to be solved
The invention aims to overcome the defect that the available instrument for directly analyzing and detecting rhenium in the copper smelting multi-component mixed waste acid cannot obtain a feasible result, and provides a novel accurate detection method for rhenium in the copper smelting multi-component mixed waste acid. By adopting the technical scheme, the defects of large influence of impurity ions, serious matrix effect, larger deviation of detection results, poor environmental protection, longer period and the like in the process of analyzing and detecting rhenium in the copper smelting multi-component mixed waste acid in the prior art can be effectively overcome, the rapid detection is realized, and the technical support is provided for enrichment and purification of rhenium in the copper smelting multi-component mixed waste acid.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention discloses a method for accurately detecting rhenium in copper smelting multi-element mixed waste acid, which comprises the following steps of:
step one, pretreatment of resin
Soaking and swelling the polystyrene divinyl benzene type organic amine macroporous anion exchange resin by water, and sequentially performing washing, alkaline soaking and transformation, washing and acid soaking and transformation after swelling is finished;
step two, absorbing rhenium in the copper smelting multi-element mixed waste acid
Firstly, filtering a tested copper smelting multi-component mixed waste acid sample, and then transferring rhenium in the filtered multi-component mixed waste acid sample to the resin in the step one in a static adsorption or dynamic adsorption mode;
step three, resolving rhenium rich resin
Washing the resin after absorbing rhenium, and then adopting a rhenium analysis agent to analyze the washed resin to obtain a rhenium-containing analysis solution;
step four, detecting the rhenium content
And (3) washing the resolved resin to obtain a washing solution, performing constant volume on the washing solution and the rhenium-containing resolving solution in the third step, and then directly detecting the rhenium content by adopting a spectrophotometry method or an ICP-AES method.
Furthermore, the resin in the first step is immersed in distilled water for swelling for 10-24h, the resin is washed by the distilled water after swelling is finished, and then the resin is statically immersed and transformed by NaOH or ammonia water for 12-24h, wherein the mass percentage concentration of NaOH and ammonia water is 1-10%; and after the transformation is finished, washing the resin by using distilled water, then immersing and transforming for 12-24 hours by using sulfuric acid, hydrochloric acid or a mixed acid of the sulfuric acid and the hydrochloric acid, wherein the mass percentage concentration of the sulfuric acid and the hydrochloric acid is 5-15%, and washing after the transformation is finished.
Furthermore, the tested copper smelting multielement mixed waste acid sample in the step two is filtered by adopting qualitative slow filter paper or quantitative fast filter paper.
Furthermore, in the second step, stirring static adsorption is adopted when the volume of the multi-component mixed waste acid sample is not more than 1000ml, stirring adsorption is carried out for 10-60min when the liquid-solid volume ratio of the sample to the resin is 20: 1-40: 1, and dynamic adsorption is adopted when the volume of the multi-component mixed waste acid sample is 1-20L, wherein the dynamic adsorption rate is 5-15 BV/h.
Furthermore, in the third step, the resin after absorbing rhenium is washed until the pH value of an effluent liquid is 3-6, and then ammonia water or sodium hydroxide is adopted as a rhenium analysis agent to analyze the washed resin, wherein the mass percent concentration of the ammonia water analysis agent is 1.0-5.0%, and the mass percent concentration of the sodium hydroxide analysis agent is 2-10%.
Furthermore, when the rhenium on the resin is transferred into the solution by adopting a static adsorption mode in the step two, the liquid-solid volume ratio of the rhenium resolving agent to the resin in the step three is 1: 1-2: 1, the static analysis time is 10-120 min; when rhenium on the resin is transferred into the solution in the second step by adopting a dynamic adsorption mode, the rhenium resolving agent is used for transferring at the resolving rate of 0.5-5BV/h, and the amount of the transfer liquid is preferably 2-6 BV.
Furthermore, when ammonia water is used as a rhenium analysis agent in the rhenium transfer resin in the third step, the rhenium-containing analysis liquid obtained in the fourth step is used for detecting the rhenium content by adopting a spectrophotometry or ICP-AES; when sodium hydroxide is used as the rhenium analysis agent in the rhenium transfer resin in the third step, the rhenium-containing analysis liquid obtained in the fourth step is preferably subjected to spectrophotometry to detect the rhenium content.
Furthermore, when the rhenium content is detected by adopting a spectrophotometry in the fourth step, firstly, a small amount of phenolphthalein or thymolphthalein is dripped into the constant volume liquid, if the solution is red or blue, an HCl solution is dripped until the solution is colorless, if the solution is colorless, firstly, analytically pure concentrated ammonia water is dripped until the solution is colorless, and then, the HCl solution is dripped until the solution is colorless; then adding tartaric acid or citric acid as masking agent, adding tin dichloride as reducing agent and dimethylglyoxime as color developing agent in hydrochloric acid system, shaking uniformly after constant volume for a period of time, and then directly detecting rhenium content by adopting spectrophotometry or ICP-AES method.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention relates to an accurate detection method of rhenium in copper smelting multi-component mixed waste acid, which comprises four steps of resin pretreatment, rhenium adsorption in the copper smelting multi-component mixed waste acid, resin-rich rhenium desorption and rhenium content detection.
(2) According to the accurate detection method for rhenium in the copper smelting multi-component mixed waste acid, the polyphenyl-alkene divinyl benzene type organic amine macroporous anion exchange resin is specifically selected as an adsorbent to efficiently adsorb and transfer rhenium elements from the copper smelting multi-component mixed waste acid, so that various metal ions and acid radical ions in the waste acid do not influence the transfer of rhenium, impurities in a sample are efficiently separated, and the detection of the rhenium content in the subsequent copper smelting multi-component mixed waste acid is facilitated; the selected resin has strong anti-pollution capability, high adsorption capacity and long service life, and the adsorption and desorption capabilities of the resin are not obviously weakened within 1 year of experimental recycling.
(3) According to the accurate detection method for rhenium in the copper smelting multi-element mixed waste acid, the target element rhenium is transferred in a static adsorption or dynamic adsorption mode flexibly selected according to the content of rhenium in the copper smelting multi-element mixed waste acid, and specific parameters in the adsorption process are optimized, so that the adsorption effect of rhenium in the multi-element mixed waste acid is further effectively improved, the resin after rhenium is adsorbed can flexibly select an analysis process, and the method is simple and convenient in operation process, short in time, good in flexibility and high in efficiency.
(4) According to the accurate detection method for rhenium in the copper smelting multi-element mixed waste acid, ammonia water or sodium hydroxide can be flexibly selected for analysis, two kinds of analysis liquid are detected by different instruments, the accuracy of the result is convenient to guarantee, and meanwhile specific parameters in the analysis process are optimized, so that the obtained solution can be conveniently analyzed by different instruments, the comparison of a subsequent detection method is further facilitated, and the accuracy and precision of detection are improved.
(5) According to the accurate detection method for rhenium in the copper smelting multi-component mixed waste acid, the adsorbent of the rhenium element in the copper smelting multi-component mixed waste acid and the overall detection process of rhenium are strictly controlled, so that low-concentration rhenium in the multi-component mixed waste acid can be enriched, the enrichment multiple is high, the next detection method can be conveniently selected, and the detection sensitivity and accuracy are further improved. The waste acid sample sampling amount of the detection method is large, the waste acid sample sampling amount is few, namely hundreds of milliliters, and the waste acid sample sampling amount is more than tens of liters, the sample representativeness is stronger compared with the traditional method for sampling from a few milliliters to a few tens of milliliters, pure rhenium-containing liquid with different concentrations can be obtained through enrichment, the operation is simple, the result is stable and good in accuracy, the method can be flexibly and variously adapted to different samples, and can be popularized and applied to detection of rhenium in waste acids in other similar industries.
Detailed Description
Because the multi-element mixed waste acid for copper smelting contains impurities such as copper, lead, zinc, mercury, selenium, fluorine, chlorine, arsenic, rhenium, thallium and the like under high sulfuric acid concentration, the impurities are various, the difference of high content and low content is large, the rhenium content of a target element is low, and strong matrix effect and spectrum interference can be generated in the instrument analysis process, so that the detection result deviation is large or a sample cannot be detected, and a feasible result is difficult to obtain.
Based on the problems, the invention provides a novel method for accurately detecting rhenium in copper smelting multi-component mixed waste acid, which comprises four steps of resin pretreatment, adsorption of rhenium in the copper smelting multi-component mixed waste acid, analysis of rich-loading resin rhenium and detection of rhenium content. According to the invention, the polyphenyl divinyl benzene type organic amine macroporous anion exchange resin is selected as the adsorbent to efficiently adsorb and transfer the rhenium element from the copper smelting multi-element mixed waste acid, so that the influence of impurity ions in the multi-element mixed waste acid is effectively reduced, the impurities in a sample are efficiently separated, the detection of the rhenium content in the subsequent copper smelting multi-element mixed waste acid is facilitated, the selected resin has strong anti-pollution capacity, high adsorption capacity and long service life, and the adsorption and desorption capacity of the resin is not obviously weakened within 1 year of experimental recycling.
In addition, the method can also flexibly select a static adsorption or dynamic adsorption mode to transfer the target element rhenium according to the content of rhenium in the copper smelting multi-element mixed waste acid, and the resin after absorbing rhenium can also flexibly select ammonia water or sodium hydroxide to analyze, so that the adsorption and analysis effects of rhenium in the multi-element mixed waste acid are further effectively improved, the obtained solution can be conveniently analyzed by different instruments, the comparison of a subsequent detection method is further facilitated, and the detection accuracy and precision are improved. The invention also optimizes specific processes and parameters in the adsorption and analysis processes, thereby further improving the adsorption and analysis effects of rhenium in the waste acid and facilitating the subsequent detection of rhenium. According to the invention, the overall detection process of rhenium in the copper smelting multi-component mixed waste acid is improved, so that low-concentration rhenium in the multi-component mixed waste acid can be enriched, the enrichment multiple is high, the flexibility is strong, the detection sensitivity and accuracy are good, the sample volume of a waste acid sample is large, the representativeness is stronger, pure rhenium-containing liquid with different concentrations can be enriched, and a powerful technical support is provided for enrichment and purification of rhenium in the copper smelting multi-component mixed waste acid.
Specifically, the accurate detection method for rhenium in the copper smelting multielement mixed waste acid comprises the following steps:
step one, pretreatment of resin
Soaking a polyphenylene divinyl benzene type organic amine macroporous anion exchange resin in distilled water for swelling for 10-24h, washing soluble impurities and broken resin by using distilled water after swelling is finished, and then statically soaking and transforming for 12-24h by using NaOH or ammonia water, wherein the mass percentage concentration of NaOH and ammonia water is 1-10%; and after the transformation is finished, washing the resin to be neutral by using distilled water, then immersing and transforming for 12-24 hours by using sulfuric acid, hydrochloric acid or a mixed acid of the sulfuric acid and the hydrochloric acid, wherein the mass percentage concentration of the sulfuric acid and the hydrochloric acid is 5-15%, and washing to be acidic after the transformation is finished.
In the first step, the polyphenylene divinyl benzene type organic amine macroporous anion exchange resin is used as a high-efficiency selective adsorbent for rhenium in the copper smelting multi-component mixed waste acid, and the specific model of the resin can be Z407; the functional group of the Z407 resin is primary amino, the granularity is 0.8-1.3mm, the water content is 45-50%, and the specific gravity is 0.9-1.0.
Step two, absorbing rhenium in the copper smelting multi-element mixed waste acid
Firstly, filtering a tested copper smelting multielement mixed waste acid sample by using qualitative slow filter paper or quantitative fast filter paper to ensure that the particulate matter is less than 30ppm and no turbidity is caused by visual inspection. The selection of the two types of filter paper is mainly determined according to the state of a sample, and if the sample is clear and has no suspended matters by visual inspection, quantitative quick filter paper is preferably adopted for filtering; if the sample is cloudy, black or red when viewed visually, a qualitative slow filter paper is preferably used for filtration. And then transferring rhenium in the filtered multi-element mixed waste acid sample to the resin in the step one by adopting a static adsorption or dynamic adsorption mode.
When the volume of the multi-component waste acid sample is not more than 1000ml, stirring static adsorption is adopted, and the liquid-solid volume ratio of the sample to the resin is 20: 1-40: 1, stirring adsorption is carried out for 10-60min, when the volume of the multi-component waste acid sample is 1-20L, dynamic adsorption is adopted, the pretreated resin is filled into a transparent glass standard port adsorption column, the filtered multi-component waste acid sample slowly passes through the adsorption column from top to bottom, and the rhenium in the multi-component waste acid sample is adsorbed by the resin in the adsorption column, wherein the dynamic adsorption rate is 5-15 BV/h.
In the second step, rhenium in the waste acid is transferred to the Z407 resin by adopting a static adsorption or dynamic adsorption mode with the pretreated Z407 resin, and various impurity ions such As Cu, Fe, Zn, Cl, F, As, S and the like in the waste acid in the process do not influence the transfer of rhenium, so that the impurity ions in the waste acid can be efficiently separated from target elements, and the influence of the impurity ions in the process of carrying out direct sample treatment-instrument analysis and detection on the copper smelting multi-component mixed waste acid is effectively avoided.
Step three, resolving rhenium rich resin
Washing the resin after absorbing rhenium to remove impurity ions and residual waste acid, washing until the pH value of an effluent liquid is 3-6, adopting ammonia water or sodium hydroxide as a rhenium analysis agent to analyze the washed resin, and transferring rhenium on the resin into a solution to obtain a rhenium-containing analysis liquid; the volume of the rhenium-containing analytic solution is only 1-20% of the volume of the multi-element mixed waste acid sample, and the volume of the rhenium-containing analytic solution is greatly reduced compared with the sample volume, so that the concentration of rhenium can be effectively improved, and the accuracy of analysis and detection can be conveniently improved.
The mass percentage concentration of the ammonia water resolving agent in the third step is 1.0-5.0%, preferably 2-4%; the mass percentage concentration of the sodium hydroxide resolving agent is 2-10%, and the preferred mass percentage concentration is 4-6%. When rhenium on the resin is transferred into the solution in the second step by adopting a static adsorption mode, the liquid-solid volume ratio of the rhenium resolving agent to the resin is 1: 1-2: 1, preferably 1.5: 1, the static transfer time is 10-120min, preferably 20-40 min; when rhenium on the resin is transferred into the solution by dynamic adsorption in the second step, the rhenium resolving agent is used for transferring at a resolving rate of 0.5-5BV/h, preferably 2-3BV/h, and the amount of the transfer liquid is preferably 2-6BV (the unit of the adsorption rate and resolving rate of the invention is BV/h, but BV is also used as the unit of the rate in practice, which is also the result of the convention). Static adsorption transfer is further optimized by the two adsorption modes, so that the operation time can be saved, and the detection efficiency is improved.
Step four, detecting the rhenium content
The method comprises the steps of washing the resolved resin to obtain a washing liquid, performing constant volume on the washing liquid and the rhenium-containing resolving liquid in the third step, and then directly detecting the rhenium content by adopting a spectrophotometric method or an ICP-AES method, wherein in the detection process of the spectrophotometric method, in order to keep the acidity consistency of a sample, 2 drops of 0.1% phenolphthalein or thymolphthalein are firstly dropped into the constant volume liquid, if the solution is red or blue, an HCl solution (one part of hydrochloric acid plus three parts of water) is dropped to be colorless, if the solution is colorless, analytically pure concentrated ammonia water is firstly dropped to be colored, then the HCl solution (one part of hydrochloric acid plus three parts of water) is dropped to be colorless, then tartaric acid or citric acid with the concentration of 300-500 g/L is added as a masking agent, tin dichloride with the concentration of 200-250 g/L is added into a hydrochloric acid system as a reducing agent, dimethylglyoxime with the concentration of 10 g/L is added as a photometer, shaking is performed for standing for a period of constant volume, then the absorbance is measured at a 450nm position by adopting.
When ammonia water is used as a rhenium analysis agent to transfer rhenium in the resin in the third step, detecting the rhenium content of the obtained rhenium-containing analysis liquid by adopting a spectrophotometry or an ICP-AES (inductively coupled plasma-atomic emission Spectrometry) method in the fourth step; when sodium hydroxide is used as a rhenium resolving agent to transfer rhenium in the resin in the third step, the rhenium-containing resolving liquid obtained in the fourth step is preferably subjected to spectrophotometry to detect the rhenium content, so that flame interference of sodium ions on ICP-AES is avoided.
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Pretreatment process of resin: weighing 100ml of Z407 resin, pouring the Z407 resin into a 200ml beaker, adding distilled water, immersing and swelling for 10 hours at normal temperature, pouring the resin into a 60-mesh stainless steel sieve after swelling, washing with distilled water and sieving out the crushed resin, adding the resin into the 200ml beaker, adding 1% sodium hydroxide solution, immersing the resin for 12 hours, washing the resin with distilled water after immersing until the pH value is 7, adding 15% sulfuric acid, immersing for 12 hours, and washing the resin with distilled water until the pH value is 5-7 for later use.
Weighing 500ml of copper smelting multielement mixed waste acid sample filtered by qualitative slow filter paper, adding the sample into a 1L beaker, and adding H in the copper smelting multielement mixed waste acid sample2SO4The content of 5.1 percent, 2.4 g/L percent of fluorine, 3.3 g/L percent of chlorine, 2.0 g/L percent of arsenic, 21ppm of lead, 210ppm of zinc and 260ppm of copper, 25ml of the pretreated Z407 resin is added into the beaker, the speed is electrically stirred and controlled to be 350rpm, the stirring and adsorption time is 10min, a 40-mesh stainless steel sieve is used for sieving the resin after the adsorption is finished, distilled water is used for rinsing the resin until the pH value of effluent is 3, the rinsed resin is added into a 200ml beaker, 25ml of ammonia water with the concentration of 1 percent is added, and the rhenium-containing solution is obtained after 10min of stirring and desorption of rhenium.
Washing the resolved resin with distilled water until the pH value is 7-8, pouring a washing liquid and a rhenium-containing resolving liquid into a beaker, fixing the volume to 50ml, transferring 10.00ml to 200ml of the fixing volume liquid into a volumetric flask, dropwise adding 2 drops of 0.1% phenolphthalein solution, enabling the solution to be red, dropwise adding an HCl solution (one part of hydrochloric acid and three parts of water) until the solution is colorless, then adding 3ml of tartaric acid with the concentration of 300 g/L as a masking agent, adding 3ml of tin dichloride with the concentration of 200 g/L as a reducing agent into a hydrochloric acid system, adding 3ml of dimethylglyoxime with the concentration of 10 g/L as a color developing agent, shaking up and standing for 30min after the solution is fixed to a scale, measuring the absorbance at 450nm by using a spectrophotometer, detecting the rhenium content, calculating the rhenium content in the fixing volume multi-element mixture to be 70.20ppm, diluting the solution by using distilled water by 20 times, detecting the rhenium content by using AES-35.00 ppm, and calculating the rhenium content in the multi-element mixed waste acid to be 70.00 ppm.
Example 2
Pretreatment process of resin: weighing 300ml of Z407 resin, pouring into a 500ml beaker, adding distilled water, immersing and swelling for 15h at normal temperature, pouring the resin into a 60-mesh stainless steel sieve after swelling is finished, washing with distilled water and sieving out the crushed resin, adding the resin into the 500ml beaker, adding 1% ammonia water to immerse the resin for 24h, washing the resin with distilled water after immersing is finished until the pH value is 7, adding 5% hydrochloric acid to immerse for 18h, and washing the resin with distilled water after immersing is finished until the pH value is 5-7 for later use.
Filtering a copper smelting multi-component mixed waste acid sample by quantitative quick filter paper, wherein the total sample volume is 10L, no suspended substance or turbidity is caused by visual inspection, and H in the copper smelting multi-component mixed waste acid sample2SO4The method comprises the steps of preparing a rhenium-containing solution, wherein the rhenium-containing solution comprises 18.2% of fluorine, 0.9 g/L of fluorine, 1.2 g/L of chlorine, 1.5 g/L of arsenic, 19ppm of lead, 130ppm of zinc and 310ppm of copper, filling 50ml of the pretreated resin into a 20mm × 200mm transparent glass standard-mouth adsorption column, slowly adding waste acid into the adsorption column, controlling the flow rate of effluent to be 4ml/min by adjusting a valve at the lower part of the adsorption column, setting the adsorption rate to be about 5BV/h, allowing all samples to pass through the resin, washing the resin with distilled water after adsorption is finished until the pH value of the effluent is about 4, adding 5% ammonia water, analyzing at the rate of 0.5BV/h to obtain a rhenium-containing analysis solution, collecting 2-4BV rhenium-containing analysis solution to total 100ml, and fixing the volume.
Transferring 10.00ml of constant volume liquid to a 100ml volumetric flask, dropwise adding 2 drops of 0.1% thymolphthalein solution, enabling the solution to be blue, dropwise adding an HCl solution (one part of hydrochloric acid and three parts of water) until the solution is colorless, then adding 3ml of citric acid with the concentration of 300 g/L as a masking agent, adding 3ml of tin dichloride with the concentration of 250 g/L as a reducing agent into a hydrochloric acid system, adding 3ml of dimethylglyoxime with the concentration of 10 g/L as a color developing agent, shaking uniformly after the constant volume is scaled, standing for 30min, measuring the absorbance at 450nm by using a spectrophotometer, detecting the rhenium content, calculating the rhenium content in the multi-component mixed waste acid to be 2.00ppm, diluting the constant volume liquid by 10 times by using distilled water, detecting the rhenium content by using ICP-AES to be 20.20ppm, and calculating the rhenium content in the multi-component mixed waste acid to be 2.02 ppm.
Example 3
Pretreatment process of resin: weighing 100ml of Z407 resin, pouring the Z407 resin into a 200ml beaker, adding distilled water, immersing and swelling for 24h at normal temperature, pouring the resin into a 60-mesh stainless steel sieve after swelling, washing with distilled water and sieving out the crushed resin, adding the resin into the 200ml beaker, adding a 10% sodium hydroxide solution, immersing the resin for 24h, washing the resin with distilled water after immersing until the pH value is 7, and adding a 10% sulfuric acid and 10% hydrochloric acid according to a volume ratio of 1: 1 for 22 hours, and washing the resin with distilled water until the pH value is 5-7 for standby.
Measuring 900ml of copper smelting multielement mixed waste acid sample filtered by qualitative slow filter paper, adding the sample into a 2L beaker, and adding H in the copper smelting multielement mixed waste acid sample2SO456.7 percent of rhenium, 1.5 g/L percent of fluorine, 1.2 g/L percent of chlorine, 3.1 g/L percent of arsenic, 32ppm of lead, 198ppm of zinc and 450ppm of copper, 30ml of the pretreated Z407 resin is added into the beaker, the speed is electrically stirred and controlled to be 350rpm, the stirring and adsorption time is 30min, a 40-mesh stainless steel sieve is used for sieving the resin after the adsorption is finished, distilled water is used for rinsing the resin until the pH value of effluent is 5, the rinsed resin is added into a 200ml beaker, 45ml of 2 percent sodium hydroxide solution is added, and the rhenium-containing solution is obtained after 120min of stirring and desorption of rhenium.
Washing the resolved resin with distilled water until the pH value is 7-8, pouring a washing liquid and a rhenium-containing resolving liquid into a beaker, metering to 100ml, transferring 10.00ml of the metering liquid into a 100ml volumetric flask, dropwise adding 2 drops of 0.1% phenolphthalein solution, enabling the solution to be red, dropwise adding an HCl solution (one part of hydrochloric acid and three parts of water) until the solution is colorless, then adding 2.5ml of tartaric acid with the concentration of 400 g/L as a masking agent, adding 2.5ml of tin dichloride with the concentration of 220 g/L as a reducing agent into a hydrochloric acid system, adding 3ml of dimethylglyoxime with the concentration of 10 g/L as a color developing agent, shaking to a constant volume, standing for 30min, measuring the absorbance at 450nm by using a spectrophotometer, detecting the rhenium content to be 30.64ppm, and calculating the rhenium content in the multielement mixed waste acid to be 35.16 ppm.
Example 4
Pretreatment process of resin: weighing 300ml of Z407 resin, pouring into a 500ml beaker, adding distilled water, immersing and swelling for 20h at normal temperature, pouring the resin into a 60-mesh stainless steel sieve after swelling is finished, washing with distilled water and sieving out the crushed resin, adding the resin into the 500ml beaker, adding 10% ammonia water to immerse the resin for 12h, washing the resin with distilled water after immersing is finished until the pH value is 7, adding 5% hydrochloric acid to immerse for 24h, and washing the resin with distilled water until the pH value is 5-7 after immersing is finished for later use.
The copper smelting multi-component mixed waste acid sample is filtered by quantitative quick filter paper, the total sample volume is 15L, no suspended substance or turbidity is observed by eye,h in copper smelting multi-component mixed waste acid sample2SO4The method comprises the steps of preparing a rhenium-containing solution, wherein the rhenium-containing solution comprises 10.2% of fluorine, 2.2 g/L of fluorine, 2.8 g/L of chlorine, 1.1 g/L of arsenic, 67ppm of lead, 320ppm of zinc and 1201ppm of copper, filling 80ml of the pretreated resin into a 20mm × 200mm transparent glass standard-mouth adsorption column, slowly adding waste acid into the adsorption column, controlling the flow rate of effluent to be 15ml/min by adjusting a valve at the lower part of the adsorption column, setting the adsorption rate to be about 10BV/h, allowing all samples to pass through the resin, washing the resin with distilled water after adsorption is finished until the pH value of the effluent is about 5, adding 10% of sodium hydroxide solution to perform resolution at the rate of 5BV/h to obtain a rhenium-containing resolution solution, collecting 2-5BV rhenium-containing resolution solution to total 240ml, and fixing the volume.
Transferring 10.00ml of constant volume liquid to a 200ml volumetric flask, dropwise adding 2 drops of 0.1% thymolphthalein solution to obtain blue solution, dropwise adding HCl solution (one part of hydrochloric acid and three parts of water) until the solution is colorless, then adding 3ml of citric acid with the concentration of 400 g/L as a masking agent, adding 3ml of tin dichloride with the concentration of 240 g/L as a reducing agent and 3ml of dimethylglyoxime with the concentration of 10 g/L as a color developing agent into a hydrochloric acid system, shaking uniformly after the constant volume is scaled, standing for 30min, measuring the absorbance at 450nm by using a spectrophotometer, and detecting the rhenium content to be 7.99 ppm.
Example 5
Pretreatment process of resin: weighing 100ml of Z407 resin, pouring the Z407 resin into a 200ml beaker, adding distilled water, immersing and swelling for 18h at normal temperature, pouring the resin into a 60-mesh stainless steel sieve after swelling, washing with distilled water and sieving out the crushed resin, adding the resin into the 200ml beaker, adding a 5% sodium hydroxide solution, immersing the resin for 18h, washing the resin with distilled water after immersing until the pH value is 7, adding 10% sulfuric acid, immersing for 20h, and washing the resin with distilled water until the pH value is 5-7 for later use.
Measuring 1000ml of copper smelting multi-component mixed waste acid sample filtered by qualitative slow filter paper, adding the measured sample into a 1L beaker, and adding H in the copper smelting multi-component mixed waste acid sample2SO49.8% of fluorine 1.5 g/L, 1.6 g/L of chlorine, 0.9 g/L of arsenic, 59ppm of lead, 540ppm of zinc and 560ppm of copper, 25ml of the pretreated Z407 resin is added into the beaker, and the mixture is stirred electrically and controlled at a speed of 350rpm, stirring and adsorbing time is 60 min. And (3) screening out the resin by using a 40-mesh stainless steel sieve after adsorption is finished, rinsing the resin by using distilled water until the pH value of effluent is 6, adding the rinsed resin into a 200ml beaker, adding 50ml of ammonia water with the concentration of 4%, and stirring and resolving rhenium for 30min to obtain a rhenium-containing resolving solution.
Washing the resolved resin with distilled water until the pH value is 7-8, pouring a washing liquid and a rhenium-containing resolving liquid into a beaker, fixing the volume to 100ml, transferring 10.00ml to 100ml of the fixing volume liquid into a volumetric flask, dropwise adding 2 drops of 0.1% phenolphthalein solution, enabling the solution to be red, dropwise adding an HCl solution (one part of hydrochloric acid and three parts of water) until the solution is colorless, then adding 3ml of tartaric acid with the concentration of 500 g/L as a masking agent, adding 3ml of tin dichloride with the concentration of 230 g/L as a reducing agent into a hydrochloric acid system, adding 3ml of dimethylglyoxime with the concentration of 10 g/L as an ICP color developing agent, shaking up and standing for 30min after fixing the volume to a scale, measuring the absorbance at 450nm by using a spectrophotometer, detecting the rhenium content to be 15.12ppm, calculating the rhenium content to be 15.12ppm in the multivariate mixture, diluting the fixing volume by using distilled water by 10 times, detecting the rhenium content to be 15.05ppm by using AES-05 ppm, and calculating the rhenium content in the multivariate mixture to be 15.05 ppm.
Example 6
Pretreatment process of resin: weighing 300ml of Z407 resin, pouring the resin into a 500ml beaker, adding distilled water, immersing and swelling for 22h at normal temperature, pouring the resin into a 60-mesh stainless steel sieve after swelling, washing with distilled water and sieving out the crushed resin, adding the resin into the 500ml beaker, adding 2% ammonia water to immerse the resin for 20h, washing the resin with distilled water after immersing until the pH value is 7, and adding 5% sulfuric acid and 5% hydrochloric acid in a volume ratio of 1: 1 for 16h, and washing the resin with distilled water until the pH value is 5-7 for standby.
Filtering a copper smelting multi-component mixed waste acid sample by quantitative quick filter paper, wherein the total sample volume is 20L, no suspended substance or turbidity is caused by visual inspection, and H in the copper smelting multi-component mixed waste acid sample2SO4The content of fluorine is 7.6%, fluorine is 1.0 g/L, chlorine is 1.7 g/L, arsenic is 2.2 g/L, lead is 108ppm, zinc is 90ppm and copper is 110ppm, 100ml of the pretreated resin is filled into a transparent glass label with the thickness of 25mm and × 300mmSlowly adding waste acid into an adsorption column, controlling the flow rate of effluent to be 4ml/min by adjusting a valve at the lower part of the adsorption column, setting the adsorption rate to be about 15BV/h, passing all samples through resin, and washing the resin by using distilled water after adsorption is finished until the pH value of the effluent is about 6; then 5% ammonia water is added to analyze at the speed of 2.5BV/h to obtain rhenium-containing analysis solution, 2-6BV of rhenium-containing analysis solution is collected to total 400ml, and the volume is fixed.
Transferring 5.00ml of constant volume liquid to a 200ml volumetric flask, dropwise adding 2 drops of 0.1% thymolphthalein solution, enabling the solution to be blue, dropwise adding an HCl solution (one part of hydrochloric acid and three parts of water) until the solution is colorless, then adding 3ml of citric acid with the concentration of 500 g/L as a masking agent, adding 3ml of tin dichloride with the concentration of 250 g/L as a reducing agent into a hydrochloric acid system, adding 3ml of dimethylglyoxime with the concentration of 10 g/L as a color developing agent, shaking uniformly after the constant volume is scaled, standing for 30min, measuring the absorbance at 450nm by using a spectrophotometer, detecting the rhenium content to be 8.25ppm, calculating the rhenium content in the multi-component mixed waste acid to be 10.31ppm, diluting the constant volume liquid by using distilled water by 40 times, detecting the rhenium content to be 8.11ppm by using ICP-AES, and calculating the rhenium content to be 10.34 ppm.
Claims (8)
1. A method for accurately detecting rhenium in copper smelting multi-element mixed waste acid is characterized by comprising the following steps:
step one, pretreatment of resin
Soaking and swelling the polystyrene divinyl benzene type organic amine macroporous anion exchange resin by water, and sequentially performing washing, alkaline soaking and transformation, washing and acid soaking and transformation after swelling is finished;
step two, absorbing rhenium in the copper smelting multi-element mixed waste acid
Firstly, filtering a tested copper smelting multi-component mixed waste acid sample, and then transferring rhenium in the filtered multi-component mixed waste acid sample to the resin in the step one in a static adsorption or dynamic adsorption mode;
step three, resolving rhenium rich resin
Washing the resin after absorbing rhenium, and then adopting a rhenium analysis agent to analyze the washed resin to obtain a rhenium-containing analysis solution;
step four, detecting the rhenium content
And (3) washing the resolved resin to obtain a washing solution, performing constant volume on the washing solution and the rhenium-containing resolving solution in the third step, and then directly detecting the rhenium content by adopting a spectrophotometry method or an ICP-AES method.
2. The accurate detection method for rhenium in the copper smelting polybasic mixed waste acid according to claim 1, which is characterized in that: immersing the resin in the first step in distilled water for swelling for 10-24h, washing with distilled water after swelling is finished, and then statically immersing and transforming for 12-24h by adopting NaOH or ammonia water, wherein the mass percentage concentration of NaOH and ammonia water is 1-10%; and after the transformation is finished, washing the resin by using distilled water, then immersing and transforming for 12-24 hours by using sulfuric acid, hydrochloric acid or a mixed acid of the sulfuric acid and the hydrochloric acid, wherein the mass percentage concentration of the sulfuric acid and the hydrochloric acid is 5-15%, and washing after the transformation is finished.
3. The accurate detection method for rhenium in the copper smelting polybasic mixed waste acid according to claim 2, characterized in that: and filtering the detected copper smelting multielement mixed waste acid sample in the step two by adopting qualitative slow filter paper or quantitative fast filter paper.
4. The method for accurately detecting rhenium in the copper smelting waste acid mixture according to claim 3, wherein in the second step, stirring static adsorption is adopted when the volume of a waste acid mixture sample is not more than 1000ml, stirring adsorption is carried out for 10-60min when the liquid-solid volume ratio of the sample to the resin is 20: 1-40: 1, and dynamic adsorption is adopted when the volume of the waste acid mixture sample is 1-20L, and the dynamic adsorption rate is 5-15 BV/h.
5. The method for accurately detecting rhenium in the copper smelting polybasic mixed waste acid according to any one of claims 1 to 4, which is characterized in that: and in the third step, the resin after absorbing rhenium is washed until the pH value of an effluent liquid is 3-6, and then ammonia water or sodium hydroxide is adopted as a rhenium analysis agent to carry out analysis treatment on the washed resin, wherein the mass percentage concentration of the ammonia water analysis agent is 1.0-5.0%, and the mass percentage concentration of the sodium hydroxide analysis agent is 2-10%.
6. The accurate detection method for rhenium in the copper smelting polybasic mixed waste acid according to claim 5, characterized in that: when rhenium on the resin is transferred into the solution in the second step by adopting a static adsorption mode, the liquid-solid volume ratio of the rhenium resolving agent to the resin in the third step is 1: 1-2: 1, the static analysis time is 10-120 min; when rhenium on the resin is transferred into the solution in the second step by adopting a dynamic adsorption mode, the rhenium resolving agent is used for transferring at the resolving rate of 0.5-5BV/h, and the amount of the transfer liquid is preferably 2-6 BV.
7. The accurate detection method for rhenium in the copper smelting polybasic mixed waste acid according to claim 6, which is characterized in that: when ammonia water is used as a rhenium analysis agent in the third step to transfer rhenium in the resin, detecting the rhenium content of the rhenium-containing analysis liquid obtained in the fourth step by adopting a spectrophotometry or an ICP-AES method; when sodium hydroxide is used as the rhenium analysis agent in the rhenium transfer resin in the third step, the rhenium-containing analysis liquid obtained in the fourth step is preferably subjected to spectrophotometry to detect the rhenium content.
8. The accurate detection method for rhenium in the copper smelting polybasic mixed waste acid according to claim 7, which is characterized in that: when the rhenium content is detected by adopting a spectrophotometry method in the fourth step, firstly, a small amount of phenolphthalein or thymolphthalein is dripped into the constant volume liquid, if the solution is red or blue, an HCl solution is dripped until the solution is colorless, if the solution is colorless, firstly, analytically pure concentrated ammonia water is dripped until the solution is colorless, and then, the HCl solution is dripped until the solution is colorless; then adding tartaric acid or citric acid as masking agent, adding tin dichloride as reducing agent and dimethylglyoxime as color developing agent in hydrochloric acid system, shaking uniformly after constant volume for a period of time, and then directly detecting rhenium content by adopting spectrophotometry or ICP-AES method.
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