CN104176784A - Method for preparing ammonium perrhenate - Google Patents
Method for preparing ammonium perrhenate Download PDFInfo
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- CN104176784A CN104176784A CN201410403047.2A CN201410403047A CN104176784A CN 104176784 A CN104176784 A CN 104176784A CN 201410403047 A CN201410403047 A CN 201410403047A CN 104176784 A CN104176784 A CN 104176784A
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- perrhenic acid
- separating unit
- separating
- ammonium perrhenate
- flue gas
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Abstract
The invention discloses a method for preparing ammonium perrhenate, which is characterized by comprising the following steps: 1. washing and cooling flue gas generated by tungsten gold ore roasting through an eluting tower, so that perrhenic acid contained in the flue gas is dissolved in water, and the water solution containing the perrhenic acid is used for circularly eluting the roasting flue gas to increase the concentration; 2. collecting the perrhenic acid water solution, carrying out rough filtration, and carrying out nanofiltration concentration on the filtrate with nanofiltration membrane equipment to obtain a perrhenic acid nanofiltration concentrated solution; and 3. passing the perrhenic acid nanofiltration concentrated solution through continuous ion exchange equipment, eluting rhenium with a resolving agent, heating to concentrate the collected eluate at 100 DEG C, cooling, and crystallizing to obtain the ammonium perrhenate. By using the flue gas generated by tungsten gold ore roasting as the raw material, the nanofiltration membrane equipment and continuous ion exchange equipment are utilized to recover the ammonium perrhenate, thereby achieving the goals of resource recovery and environment protection; and thus, the method has favorable economic value and environmental benefit.
Description
Technical field
What the present invention relates to is to utilize nanofiltration membrane thickening equipment, continuous ion exchange apparatus from the flue gas the roasting of tungsten gold mine, to reclaim the method for H2ReO4.
Background technology
Rhenium is a kind of dissipated metal, and nature does not have simple substance rhenium, and rhenium, because having good ductility, wear resistance and the performance such as high temperature resistant, is commonly used for coating material.The application of rhenium is increasingly extensive, on market, in the state that supply falls short of demand, is mainly used in the fields such as petroleum refining catalyzer, thermoelectricity superalloy, electronic tubular construction material, aerospace specific alloy, environment protection.
Rhenium itself, without independent deposit, is often dispersed in other non-ferrous metal ore bodies, and main and molybdenum glance association coexists, and in the mineral such as micro-association and molybdenum, copper, lead, zinc, platinum, grows to vulcanize rhenium form and exists.At home, produce the enterprise of molybdenum, molybdenum glance in the time of roasting, ReS
2oxidation Re
2o
7form is enriched in cigarette ash, and the evaporation rate of rhenium is up to 60-70%, containing Re
2o
7flue gas wash through eluting column, the Re2O7 in flue gas is soluble in water, molten Re
2o
7aqueous solution cycling elution flue gas, can be enriched to certain density rhenium, therefore in molybdenum baking flue gas absorption liquid, contain a large amount of rheniums.In addition, molybdenum glance is in the time of roasting, except MoO
3outside volatilization, not yet the metallic sulfide of roasting also flows into cigarette ash with tail gas, and in cigarette ash, molybdenum is sampled high more than 40%.Consequently dilute rhenium, simultaneously again because rhenium is very similar to the character of molybdenum, make molybdenum rhenium separation difficulty, therefore domestic a lot of molybdenum manufacturing enterprise all abandons molybdenum baking flue gas absorption liquid as waste liquid, has not only polluted environment but also has caused the waste of resource.
Summary of the invention
In order to solve the recovery problem of the perrhenic acid in flue gas after the roasting of tungsten gold mine, make the perrhenic acid in flue gas obtain recycle, realize economic worth and environmental benefit, the invention provides a kind of method of utilizing nano-filtration membrane equipment, continuous ion exchange apparatus to prepare ammonium perrhenate.
For reaching technique scheme, the technical scheme that the present invention proposes is: a kind of method of preparing ammonium perrhenate, it is characterized in that, and comprise the steps:
Step 1: the flue gas that produces after the roasting of tungsten gold mine is cooling through the washing of eluting column, and the perrhenic acid containing in flue gas is soluble in water, the aqueous solution circulation that is dissolved with perrhenic acid is carried out drip washing to baking flue gas makes the concentration of perrhenic acid obtain enrichment;
Step 2: collect the perrhenic acid aqueous solution, it is concentrated that coarse filtration is carried out nanofiltration with nano-filtration membrane equipment to the aqueous solution by filtrate after filtering, and obtains perrhenic acid nanofiltration concentrated solution;
Step 3: perrhenic acid nanofiltration concentrated solution, by continuous ion exchange apparatus, carries out wash-out with resolving agent to rhenium, the elutriant of collecting is heated at 100 DEG C and concentrate, and cooling, crystallization, has just obtained ammonium perrhenate.
Further, described nanofiltration membrane molecular weight cut-off is 150-1000, and working pressure is at 10-40bar.
Further, built-in 20 separating units of described continuous ion exchange apparatus, fill anionite-exchange resin in each separating unit, and described continuous ion exchange apparatus is divided into 5 regions, and each region is composed as follows:
Adsorption zone: comprise 6 separating units, in this region, the 1st and the 2nd separating unit of 6 separating units is connected in parallel, first perrhenic acid nanofiltration concentrated solution enters the 1st, 2 of adsorption zones separating unit, perrhenic acid nanofiltration concentrated solution is through the 1st, 2 separating units, perrhenic acid part exchanges on resin, mix in the lump and enter the 3rd to the 6th separating unit being connected in the mode of two and two strings again with the water lotion of absorption water wash zone from the 1st, 2 separating unit effluent liquid, wherein the 5th, the 6th separating unit effluent liquid is the remaining liquid of absorption;
Absorption water wash zone: comprise 4 separating units, after absorption, each separating unit is washed, 4 separating units in this region connect with series system, be positioned at behind adsorption zone, separating unit rotates to behind absorption water wash zone, and the perrhenic acid not being adsorbed that is entrained in interlaminar resin is ejected by water, and the effluent liquid of the 1st, 2 separating units of effluent liquid and adsorption zone mixes the 3rd, the 4th separating unit that together enters adsorption zone;
Drying zone, anti-top: comprise 1 separating unit, with resolving the product ammonium perrhenate in district as the charging in this district, and adopt backward feed, to replace the water that is entrained in interlaminar resin, reach water of productive use reuse on the one hand, be conducive on the other hand improve product concentration;
Resolve district: comprise 5 separating units, be divided into two sections, leading portion comprises 2 separating units, back segment comprises 3 separating units, adopt the series connection of parsing agent forward to enter after 2 separating units of leading portion, its effluent liquid with resolve effluent liquid in after washing district and mix again forward and connect and enter 3 separating units of back segment, collect last separating unit fluid, obtain product ammonium perrhenate;
Resolve after washing district: comprise 4 separating units, employing is connected in series adverse current and enters pure water mode, through resolving after agent parsing, resin is by the flushing of pure water, parsing agent residual in separating unit is all washed out, and the effluent liquid of resolving in after washing district mixes with front 2 separating unit effluent liquid of resolving in district.
Further, the rotation time of described continuous ion exchange apparatus separating unit is 20-60min.
Further, resolving agent can be the mixture of ammoniacal liquor, ammonium chloride or ammoniacal liquor and ammonium chloride
Further, anionite-exchange resin can be strongly basic anion exchange resin, weak base anion-exchange resin, chelating type resin anion(R.A).
Principle of the present invention is: the flue gas producing after the roasting of tungsten gold mine is cooling through the washing of eluting column, and the perrhenic acid containing in flue gas is soluble in water, and the aqueous solution circulation that is dissolved with perrhenic acid is carried out drip washing to baking flue gas, can make the concentration of perrhenic acid obtain enrichment.Collect the perrhenic acid aqueous solution, after filtration, filtrate is concentrated the aqueous solution with nano-filtration membrane equipment; The perrhenic acid aqueous solution after concentrated, by continuous ion exchange apparatus, carries out wash-out by analytic solution to rhenium, the elutriant of collecting is heated at 100 DEG C and concentrate, and cooling, crystallization, has just obtained ammonium perrhenate.
Adopt technique scheme; the method of preparing ammonium perrhenate of the present invention; the beneficial effect having is: the present invention is taking the flue gas that produces after the roasting of tungsten gold mine as raw material; utilize nano-filtration membrane equipment and continuous ion exchange apparatus to reclaim ammonium perrhenate; reach resource recycling; the object of protection of the environment, has good economic worth and environmental benefit.
Brief description of the drawings
Fig. 1 is the method flow schematic diagram of preparing ammonium perrhenate of the present invention;
Fig. 2 is continuous ionic exchange schematic flow sheet of the present invention.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment
The method of preparing ammonium perrhenate of the present invention as shown in Figure 1, tungsten gold mine produces flue gas through roasting, after flue gas ash removal, carry out drip washing, the water that drip washing produces contains H2SO4, H2SO3, SO2, H2MoO4, H2ReO4, wherein the content of H2ReO4 is at 40-50mg/L, and getting beautiful jade wash water, to enter nanofiltration membrane concentrated, and the concentrated result of nanofiltration is as follows:
The content of the nanofiltration membrane concentrated solution perrhenic acid of experiment gained enters continuous ion exchange apparatus at 800-1000mg/L; As shown in Figure 2, built-in 20 separating units of continuous ion exchange apparatus, fill anionite-exchange resin in each separating unit, and described continuous ion exchange apparatus is divided into 5 regions, and each region is composed as follows:
Adsorption zone (5#-10#): comprise 6 separating units, in this region, 6 separating unit 5# and 6# separating unit are connected in parallel, first perrhenic acid nanofiltration concentrated solution enters adsorption zone 5# and 6# separating unit, perrhenic acid nanofiltration concentrated solution is through 5# and 6# separating unit, perrhenic acid part exchanges on resin, mix in the lump and enter the 7# being connected in the mode of two and two strings to 10# separating unit again with the water lotion of absorption water wash zone with 6# separating unit effluent liquid from 5#, wherein 9#, 10# separating unit effluent liquid are the remaining liquid of absorption;
Absorption water wash zone (1#-4#): comprise 4 separating units, after absorption, each separating unit is washed, 1#-4# separating unit in this region connects with series system, be positioned at behind adsorption zone, separating unit rotates to behind absorption water wash zone, and the perrhenic acid not being adsorbed that is entrained in interlaminar resin is ejected by water, and effluent liquid mixes with the effluent liquid of adsorption zone 5# and 6# separating unit separating unit the 7#, the 8# separating unit that together enter adsorption zone;
Anti-drying zone, top (20#): comprise 1 separating unit, with resolving the product ammonium perrhenate in district as the charging in this district, and adopt backward feed, to replace the water that is entrained in interlaminar resin, reach water of productive use reuse on the one hand, be conducive on the other hand improve product concentration;
Resolve district (15#-19#): comprise 5 separating units, be divided into two sections, leading portion comprises 15#, 16# separating unit, back segment comprises 17#, 18#, 19# separating unit, adopt the series connection of parsing agent forward to enter after 15#, 16# separating unit, its effluent liquid with resolve effluent liquid in after washing district and mix again forward and connect and enter 17#, 18#, the 19# separating unit of back segment, collect last 19# separating unit fluid, obtain product ammonium perrhenate;
Resolve after washing district (11#-14#): comprise 4 separating units, employing is connected in series adverse current and enters pure water mode, through resolving after agent parsing, resin is by the flushing of pure water, parsing agent residual in separating unit is all washed out, and the effluent liquid of resolving in after washing district mixes with front 15#, the 16# separating unit effluent liquid of resolving in district; Result is as follows:
In the above-described embodiments, only the present invention has been carried out to exemplary description, but those skilled in the art are reading after present patent application and can carry out various amendments to the present invention without departing from the spirit and scope of the present invention.
Claims (6)
1. a method of preparing ammonium perrhenate, is characterized in that, comprises the steps:
Step 1: the flue gas that produces after the roasting of tungsten gold mine is cooling through the washing of eluting column, and the perrhenic acid containing in flue gas is soluble in water, the aqueous solution circulation that is dissolved with perrhenic acid is carried out drip washing to baking flue gas makes the concentration of perrhenic acid obtain enrichment;
Step 2: collect the perrhenic acid aqueous solution, it is concentrated that coarse filtration is carried out nanofiltration with nano-filtration membrane equipment to the aqueous solution by filtrate after filtering, and obtains perrhenic acid nanofiltration concentrated solution;
Step 3: perrhenic acid nanofiltration concentrated solution is by continuous ion exchange apparatus, carries out wash-out to rhenium with ammoniacal liquor, the elutriant of collecting heat at 100 DEG C and concentrate, and cooling, crystallization, has just obtained ammonium perrhenate.
2. a kind of method of preparing ammonium perrhenate according to claim 1, is characterized in that, described nanofiltration membrane molecular weight cut-off is 150-1000, and working pressure is at 10-40bar.
3. a kind of method of preparing ammonium perrhenate according to claim 1, it is characterized in that, built-in 20 separating units of described continuous ionic exchange system, in each separating unit, fill anionite-exchange resin, described continuous ionic exchange system is divided into 5 regions, and each region is composed as follows:
Adsorption zone: comprise 6 separating units, in this region, the 1st and the 2nd separating unit of 6 separating units is connected in parallel, first perrhenic acid nanofiltration concentrated solution enters the 1st, 2 of adsorption zones separating unit, perrhenic acid nanofiltration concentrated solution is through the 1st, 2 separating units, perrhenic acid part exchanges on resin, mix in the lump and enter the 3rd to the 6th separating unit being connected in the mode of two and two strings again with the water lotion of absorption water wash zone from the 1st, 2 separating unit effluent liquid, wherein the 5th, the 6th separating unit effluent liquid is the remaining liquid of absorption;
Absorption water wash zone: comprise 4 separating units, after absorption, each separating unit is washed, 4 separating units in this region connect with series system, be positioned at behind adsorption zone, separating unit rotates to behind absorption water wash zone, and the perrhenic acid not being adsorbed that is entrained in interlaminar resin is ejected by water, and the effluent liquid of the 1st, 2 separating units of effluent liquid and adsorption zone mixes the 3rd, the 4th separating unit that together enters adsorption zone;
Drying zone, anti-top: comprise 1 separating unit, with resolving the product ammonium perrhenate in district as the charging in this district, and adopt backward feed, to replace the water that is entrained in interlaminar resin;
Resolve district: comprise 5 separating units, be divided into two sections, leading portion comprises 2 separating units, back segment comprises 3 separating units, adopt the series connection of parsing agent forward to enter after 2 separating units of leading portion, its effluent liquid with resolve effluent liquid in after washing district and mix again forward and connect and enter 3 separating units of back segment, collect last separating unit fluid, obtain product ammonium perrhenate;
Resolve after washing district: comprise 4 separating units, employing is connected in series adverse current and enters pure water mode, through resolving after agent parsing, resin is by the flushing of pure water, parsing agent residual in separating unit is all washed out, and the effluent liquid of resolving in after washing district mixes with front 2 separating unit effluent liquid of resolving in district.
4. a kind of method of preparing ammonium perrhenate according to claim 1, is characterized in that, the rotation time of described continuous ionic exchange system separating unit is 20-60min.
5. a kind of method of preparing ammonium perrhenate according to claim 1, is characterized in that, parsing agent is the mixture of ammoniacal liquor, ammonium chloride or ammoniacal liquor and ammonium chloride.
6. a kind of method of preparing ammonium perrhenate according to claim 1, is characterized in that, anionite-exchange resin is strongly basic anion exchange resin, weak base anion-exchange resin or chelating type resin anion(R.A).
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| CN201410403047.2A CN104176784B (en) | 2014-08-16 | 2014-08-16 | A kind of method preparing ammonium perrhenate |
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| CN104176784B CN104176784B (en) | 2016-03-16 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517336A (en) * | 2016-11-23 | 2017-03-22 | 西北有色金属研究院 | Method for removing rhenium from ammonium paratungstate through purification |
| CN110340377A (en) * | 2018-11-05 | 2019-10-18 | 贵研铂业股份有限公司 | A kind of method that Whote-wet method prepares high-purity platinum powder |
| CN113512644A (en) * | 2021-09-14 | 2021-10-19 | 赛恩斯环保股份有限公司 | Method for separating rhenium from ammonium molybdate solution |
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| CN101665869A (en) * | 2009-08-31 | 2010-03-10 | 厦门世达膜科技有限公司 | Method for highly concentrating metal solution in wet metallurgy |
| US20110123709A1 (en) * | 2008-06-05 | 2011-05-26 | H.C. Starck Gmbh | Process for producing pure ammonium perrhenate |
| CN102173457A (en) * | 2011-02-22 | 2011-09-07 | 辽宁大学 | Method for preparing ammonium perrhenate from waste liquid containing molybdenum and rhenium |
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2014
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Patent Citations (4)
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| US20110123709A1 (en) * | 2008-06-05 | 2011-05-26 | H.C. Starck Gmbh | Process for producing pure ammonium perrhenate |
| CN201337865Y (en) * | 2009-01-06 | 2009-11-04 | 江西铜业集团公司 | Absorption tower for recovering rhenium oxide in smoke gas |
| CN101665869A (en) * | 2009-08-31 | 2010-03-10 | 厦门世达膜科技有限公司 | Method for highly concentrating metal solution in wet metallurgy |
| CN102173457A (en) * | 2011-02-22 | 2011-09-07 | 辽宁大学 | Method for preparing ammonium perrhenate from waste liquid containing molybdenum and rhenium |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517336A (en) * | 2016-11-23 | 2017-03-22 | 西北有色金属研究院 | Method for removing rhenium from ammonium paratungstate through purification |
| CN110340377A (en) * | 2018-11-05 | 2019-10-18 | 贵研铂业股份有限公司 | A kind of method that Whote-wet method prepares high-purity platinum powder |
| CN113512644A (en) * | 2021-09-14 | 2021-10-19 | 赛恩斯环保股份有限公司 | Method for separating rhenium from ammonium molybdate solution |
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| CN104176784B (en) | 2016-03-16 |
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Application publication date: 20141203 Assignee: Xiamen Shida membrane Engineering Co.,Ltd. Assignor: XIAMEN STARMEM TECHNOLOGY CO.,LTD. Contract record no.: X2021980014823 Denomination of invention: A method for preparing ammonium rhenate Granted publication date: 20160316 License type: Exclusive License Record date: 20211221 |
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