CN104176784B - A kind of method preparing ammonium perrhenate - Google Patents
A kind of method preparing ammonium perrhenate Download PDFInfo
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- CN104176784B CN104176784B CN201410403047.2A CN201410403047A CN104176784B CN 104176784 B CN104176784 B CN 104176784B CN 201410403047 A CN201410403047 A CN 201410403047A CN 104176784 B CN104176784 B CN 104176784B
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- perrhenic acid
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Abstract
The invention discloses a kind of method preparing ammonium perrhenate, comprise the steps: step 1: the flue gas produced after molybdenum glance roasting cools through the washing of eluting column, the perrhenic acid contained in flue gas is soluble in water, and the water solution cycle being dissolved with perrhenic acid carries out drip washing to baking flue gas makes the concentration of perrhenic acid obtain enrichment; Step 2: collect the perrhenic acid aqueous solution, filtrate is carried out nanofiltration with nano-filtration membrane equipment to the aqueous solution after filtering and is concentrated by coarse filtration, obtains perrhenic acid nanofiltration concentrated solution; Step 3: perrhenic acid nanofiltration concentrated solution, by continuous ion exchange apparatus, carries out wash-out with parsing agent to rhenium, and heated by the elutriant collected concentrated at 100 DEG C, cooling, crystallization, just obtain ammonium perrhenate.The present invention for raw material with the flue gas produced after molybdenum glance roasting, utilizes nano-filtration membrane equipment and continuous ion exchange apparatus to reclaim ammonium perrhenate, reaches resource recycling, the object of protection of the environment, have good economic worth and environmental benefit.
Description
Technical field
What the present invention relates to is utilize nanofiltration membrane thickening equipment, continuous ion exchange apparatus to reclaim H from the flue gas after molybdenum glance roasting
2reO
4method.
Background technology
Rhenium is a kind of dissipated metal, and nature does not have simple substance rhenium, and rhenium, because having excellent ductility, wear resistance and the performance such as high temperature resistant, is commonly used for coating material.The application of rhenium is increasingly extensive, is commercially 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 mainly with in the mineral such as micro-association and molybdenum, copper, lead, zinc, platinum, long exist with sulfuration rhenium form.At home, produce the enterprise of molybdenum, molybdenum glance when roasting, ReS
2oxidation Re
2o
7form is enriched in cigarette ash, the evaporation rate of rhenium 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
7water solution cycle drip washing flue gas, certain density rhenium can be enriched to, therefore in molybdenum baking flue gas absorption liquid containing a large amount of rhenium.In addition, molybdenum glance when roasting, except MoO
3outside volatilization, the metallic sulfide of not yet roasting also flows into cigarette ash with tail gas, and in cigarette ash, molybdenum taste is high by more than 40%.Consequently namely dilute rhenium, simultaneously again because rhenium is very similar to the character of molybdenum, make molybdenum rhenium separation difficulty, molybdenum baking flue gas absorption liquid all abandons as waste liquid by therefore domestic a lot of molybdenum manufacturing enterprises, not only pollutes environment but also causes the waste of resource.
Summary of the invention
In order to solve the recovery problem of the perrhenic acid after molybdenum glance roasting in flue gas, the perrhenic acid in flue gas is made to obtain recycle, realize economic worth and environmental benefit, the invention provides a kind of nano-filtration membrane equipment, continuous ion exchange apparatus of utilizing to prepare the method for ammonium perrhenate.
For reaching technique scheme, the technical scheme that the present invention proposes is: a kind of method preparing ammonium perrhenate, is characterized in that, comprise the steps:
Step 1: the flue gas produced after molybdenum glance roasting cools through the washing of eluting column, and the perrhenic acid contained in flue gas is soluble in water, the water solution cycle being dissolved with perrhenic acid carries out drip washing to baking flue gas makes the concentration of perrhenic acid obtain enrichment;
Step 2: collect the perrhenic acid aqueous solution, filtrate is carried out nanofiltration with nano-filtration membrane equipment to the aqueous solution after filtering and is concentrated by coarse filtration, obtains perrhenic acid nanofiltration concentrated solution;
Step 3: perrhenic acid nanofiltration concentrated solution, by continuous ion exchange apparatus, carries out wash-out with parsing agent to rhenium, and heated by the elutriant collected concentrated at 100 DEG C, cooling, crystallization, just obtain 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, 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, 6 separating units the 1st and the 2nd separating unit is connected in parallel, first perrhenic acid nanofiltration concentrated solution enters the 1st, 2, adsorption zone separating unit, perrhenic acid nanofiltration concentrated solution is through the 1st, 2 separating unit, perrhenic acid part exchanges on resin, mix in the lump from the water lotion of the 1st, 2 separating unit effluent liquid and absorption water wash zone and enter with two and the 3 to the 6 separating unit being connected of two modes of go here and there again, wherein the 5th, the 6th separating unit effluent liquid is liquid more than absorption;
Absorption water wash zone: comprise 4 separating units, after absorption, each separating unit is washed, 4 separating units in this region connect in a series arrangement, after being positioned at adsorption zone, after separating unit rotates to absorption water wash zone, be entrained in not ejected by water by the perrhenic acid adsorbed of interlaminar resin, the effluent liquid of effluent liquid and adsorption zone the 1st, 2 separating units mixes the 3rd, the 4th separating unit together entering adsorption zone;
Drying zone, anti-top: comprise 1 separating unit, with the charging of product ammonium perrhenate as this district of resolving district, and adopts backward feed, to replace the water being entrained in interlaminar resin, reaches water of productive use reuse on the one hand, be conducive on the other hand improving 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, after adopting the series connection of parsing agent forward to enter leading portion 2 separating units, its effluent liquid and the effluent liquid of resolving in after washing district mix forward again 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, after resolving agent and resolving, resin is by the flushing of pure water, the parsing agent remained in separating unit all washed out, 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, the mixture that agent can be ammoniacal liquor, ammonium chloride or ammoniacal liquor and ammonium chloride is resolved
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 produced after molybdenum glance roasting cools through the washing of eluting column, and the perrhenic acid contained in flue gas is soluble in water, and the water solution cycle being dissolved with perrhenic acid carries out drip washing to baking flue gas, and the concentration of perrhenic acid can be made to 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, and heated by the elutriant collected concentrated at 100 DEG C, cooling, crystallization, just obtain ammonium perrhenate.
Adopt technique scheme; the method preparing ammonium perrhenate of the present invention; the beneficial effect had is: the present invention with the flue gas produced after molybdenum glance roasting for 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.
Accompanying drawing explanation
Fig. 1 is the method flow schematic diagram preparing ammonium perrhenate of the present invention;
Fig. 2 is that continuous ionic of the present invention exchanges schematic flow sheet.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment
As shown in Figure 1, molybdenum glance produces flue gas through roasting to the method preparing ammonium perrhenate of the present invention, after flue gas ash removal, carries out drip washing, and the water that drip washing produces contains H
2sO
4, H
2sO
3, SO
2, H
2moO
4, H
2reO
4, wherein H
2reO
4content at 40-50mg/L, get beautiful jade wash water enter nanofiltration membrane concentrate, it is as follows that nanofiltration concentrates result:
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, 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 from the water lotion of 5# with 6# separating unit effluent liquid and absorption water wash zone and enter with two and 7# to the 10# separating unit that is connected of two modes of go here and there again, wherein 9#, 10# separating unit effluent liquid is liquid more than 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 in a series arrangement, after being positioned at adsorption zone, after separating unit rotates to absorption water wash zone, be entrained in not ejected by water by the perrhenic acid adsorbed of interlaminar resin, effluent liquid mixes with the effluent liquid of adsorption zone 5# and 6# separating unit separating unit 7#, 8# separating unit together entering adsorption zone;
Drying zone, anti-top (20#): comprise 1 separating unit, with the charging of product ammonium perrhenate as this district of resolving district, and adopt backward feed, to replace the water being entrained in interlaminar resin, reach water of productive use reuse on the one hand, be conducive on the other hand improving 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, after adopting the series connection of parsing agent forward to enter 15#, 16# separating unit, its effluent liquid and the effluent liquid of resolving in after washing district mix forward again and connect and enter 17#, 18#, 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, after resolving agent and resolving, resin is by the flushing of pure water, the parsing agent remained in separating unit all washed out, the effluent liquid of resolving in after washing district mixes with front 15#, 16# separating unit effluent liquid of resolving in district; Result is as follows:
In the above-described embodiments, only to invention has been exemplary description, but those skilled in the art can carry out various amendment to the present invention without departing from the spirit and scope of the present invention after reading present patent application.
Claims (5)
1. prepare a method for ammonium perrhenate, it is characterized in that, comprise the steps:
Step 1: the flue gas produced after molybdenum glance roasting cools through the washing of eluting column, and the perrhenic acid contained in flue gas is soluble in water, the water solution cycle being dissolved with perrhenic acid carries out drip washing to baking flue gas makes the concentration of perrhenic acid obtain enrichment;
Step 2: collect the perrhenic acid aqueous solution, filtrate is carried out nanofiltration with nano-filtration membrane equipment to the aqueous solution after filtering and is concentrated by coarse filtration, obtains perrhenic acid nanofiltration concentrated solution;
Step 3: perrhenic acid nanofiltration concentrated solution, by continuous ionic exchange system, carries out wash-out with ammoniacal liquor to rhenium, heated by the elutriant collected concentrated at 100 DEG C, cooling, crystallization, just obtain ammonium perrhenate;
Built-in 20 separating units of described continuous ionic exchange system, fill anionite-exchange resin in each separating unit, 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, 6 separating units the 1st and the 2nd separating unit is connected in parallel, first perrhenic acid nanofiltration concentrated solution enters the 1st, 2, adsorption zone separating unit, perrhenic acid nanofiltration concentrated solution is through the 1st, 2 separating unit, perrhenic acid part exchanges on resin, mix in the lump from the water lotion of the 1st, 2 separating unit effluent liquid and absorption water wash zone and enter with two and the 3 to the 6 separating unit being connected of two modes of go here and there again, wherein the 5th, the 6th separating unit effluent liquid is liquid more than absorption;
Absorption water wash zone: comprise 4 separating units, after absorption, each separating unit is washed, 4 separating units in this region connect in a series arrangement, after being positioned at adsorption zone, after separating unit rotates to absorption water wash zone, be entrained in not ejected by water by the perrhenic acid adsorbed of interlaminar resin, the effluent liquid of effluent liquid and adsorption zone the 1st, 2 separating units mixes the 3rd, the 4th separating unit together entering adsorption zone;
Drying zone, anti-top: comprise 1 separating unit, with the charging of product ammonium perrhenate as this district of resolving district, and adopts backward feed, to replace the water being 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, after adopting the series connection of parsing agent forward to enter leading portion 2 separating units, its effluent liquid and the effluent liquid of resolving in after washing district mix forward again 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, after resolving agent and resolving, resin is by the flushing of pure water, the parsing agent remained in separating unit all washed out, the effluent liquid of resolving in after washing district mixes with front 2 separating unit effluent liquid of resolving in district.
2. a kind of method 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 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.
4. a kind of method 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.
5. a kind of method 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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| CN106517336B (en) * | 2016-11-23 | 2018-03-09 | 西北有色金属研究院 | A kind of purification from ammonium paratungstate is except the method for rhenium |
| CN110340377B (en) * | 2018-11-05 | 2022-11-29 | 贵研铂业股份有限公司 | Method for preparing high-purity platinum powder by full-wet method |
| CN113512644B (en) * | 2021-09-14 | 2021-11-26 | 赛恩斯环保股份有限公司 | Method for separating rhenium from ammonium molybdate solution |
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|---|---|---|---|---|
| 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 |
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| DE102008026910A1 (en) * | 2008-06-05 | 2009-12-10 | H.C. Starck Gmbh | Process for the preparation of pure ammonium barrier phenate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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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 |