CN1083802C

CN1083802C - Elimination of molybdenum from tungstate soltuion

Info

Publication number: CN1083802C
Application number: CN98122929A
Authority: CN
Inventors: 肖连生; 张启修; 龚柏凡
Original assignee: Central South University
Current assignee: Central South University
Priority date: 1998-12-05
Filing date: 1998-12-05
Publication date: 2002-05-01
Anticipated expiration: 2018-12-05
Also published as: CN1256245A

Abstract

The present invention belongs to the field of the purification of metallurgy inorganic matters in chemical industry, which is characterized in that a dense moving bed and a fluidized bed are used for replacing a fixed bed for treating tungstate solution pretreated by thiolysis, the serialization of an adsorption process is realized, and the danger of the burnout of resin because of too high temperature rise in the process of the analysis of molybdenum is eliminated; due to the full utilization of an analysis agent, the consumption of chemical reagents is reduced. The present invention has the advantages of convenient operation, simple equipment and low investment, and an optimal molybdenum removing effect can be obtained in a large production scale.

Description

From tungstate solution, remove the method for molybdenum

The invention belongs to chemical industry metallurgical inorganics purification field.

In existing tungsten isolation technique, has best application prospect based on class methods that generate Thiomolybdate, except continuing to use for a long time but there is the MoS of certain drawback ₃Outside the precipitator method, a kind of method of the industrial application of having succeedd is an ion exchange method, yet,

The ion exchange method that CN88105712.6 proposes, its operational procedure be,, leaks to wear to molybdenum and stop absorption directly by anion exchange resin bed through the pretreated tungstate solution of thioated.Again to contain finite concentration Cl ^-Ionic chloride solution drip washing resin, leacheate is merged into the tungstate solution that removes molybdenum with handing over back liquid.The resin of load molybdenum is resolved molybdenum with oxidizing solution, returns absorption after regeneration.If the ammonium tungstate system, processing be through purify removing P, As, the ammonium tungstate solution behind the Si, product liquid directly send crystalline A PT product; If the sodium wolframate system, what obtain removes molybdenum liquid again through further handling to reclaim tungsten.This technology is usually said two step method.

The ion-exchange one-stage that CN93111497.7 proposes separates P, As, and Si, Mo produce the technology of ammonium tungstate, look the height of object solution molybdenum content, adopt single-column method or multicolumn series process.Use the single-column method when molybdenum content is low, it is that tungsten is co-adsorption, and wearing with the tungsten leakage is terminal point, and substep is resolved again, promptly earlier with NH ₄Cl-NH ₄OH solution is resolved tungsten, and product liquid direct crystallization APT product is resolved molybdenum with the sodium hypochlorite solution alkaline again, and resin obtains regeneration simultaneously, enters the lower whorl adsorption operation after cleaning; Use the multicolumn method when molybdenum content is high, in one need not turned the continuous exchange process that is, molybdenum was adsorbed in respectively on the different exchanging column resins with tungsten, divided post to resolve molybdenum and tungsten then.Resolve molybdenum and use the sodium hypochlorite solution alkaline, resolve tungsten NH ₄Cl-NH ₄The product liquid direct crystallization APT product of OH solution, tungsten.This technology is usually said single stage method.

The above existing ion-exchange removes molybdenum technology and all is to use fixed-bed ion exchange technology.Because it adopts oxidizing solution to resolve molybdenum, be the heat release reaction, often when scale operation, just produce the danger that burns out resin because of temperature rise is too high.

The objective of the invention is to overcome the deficiencies in the prior art part, and a kind of adsorption process serialization that can realize is provided, parsing is even, abundant, productive rate is high, cost is low, the molybdenum removing technology of reduced investment.

Technical scheme of the present invention is: adopt packed moving bed and fluidized-bed ion exchange technique to remove molybdenum, see accompanying drawing.

The absorption molybdenum carries out object solution in packed moving bed 1---and the thioated feed liquid enters continuously from the cylinder bottom, by being duration of contact 20～100min control feed liquor speed, removes molybdenum liquid and overflows from the resin bed top; The resin of saturated load molybdenum is regularly emitted from the cylinder bottom in batches, and the regenerating resin of same amount adds from the cylinder top simultaneously; Every batch of discharging amount of saturated resin is 1/8～1/10 of the total loading capacity of resin; Meanwhile, resin after the regeneration of the additional equal amts in column top is to keep the former height of resin bed; The every batch of resin is emitted and by resin the saturated adsorption capacity of molybdenum and unit time is advanced post molybdenum amount pitch time and calculate and determine;

Resolve molybdenum and regeneration of resin and in fluidized-bed 2, carry out, the tungsten that flush away is carried secretly behind the resin input fluidized-bed of saturated load molybdenum, washings returns batching; Resolve molybdenum with the sodium hypochlorite solution alkaline again; Resolve operation from the bottom feed liquor, the top fluid, feed liquor speed can suspend with resin or fluidised form turns to principle; Resolve agent NaClO concentration 0.4～1.0mol/L, the outlet liquid temp is controlled at below 60 ℃ during parsing; Molybdenum is resolved the back and is used the regenerator process resin, and regenerator is for containing Cl ^-The chloride solution of 80～120g/L, the resin through resolving regeneration has recovered the resinogen color and luster, and loading capacity is stable, returns absorption next time.

The feature of molybdenum removing technology of the present invention also is:

Object solution is through the pretreated tungstate solution of thioated, comprises sodium tungstate solution and ammonium tungstate solution, its feed liquor WO ₃Concentration is: ammonium tungstate solution 100～300g/L, sodium tungstate solution 20～200g/L.

Ion exchange resin is that anionite-exchange resin comprises macroporous type and gel type strong base and weak base anion-exchange resin.

The present invention compares with fixed-bed ion exchange molybdenum removing technology has following advantage.

1. what packed moving bed 1 had many series connection fixed beds removes the molybdenum effect, can realize the serialization of adsorption process, can make full use of the loading capacity of resin, reduces the co-adsorption loss of tungsten.

2. resolve molybdenum with fluidized-bed 2, can effectively control temperature in the cylinder, eliminated the danger that burns out resin because of temperature rise is too high; Resolve evenly, abundant, no dead angle, the regenerating resin absorption property is stable.

3. resolving agent can make full use of, and reagent consumption reduces, and improves the concentration of molybdenum in the desorbed solution simultaneously, is convenient to reclaim.

4. entrained solid contaminant particles in can timely and effective removing resin layer.

5. the raising productive rate reduces required amount of resin significantly, reduces investment outlay.

Description of drawings: accompanying drawing is packed moving bed and fluidized-bed connection diagram, has showed its technical process situation.

Embodiment:

Embodiment 1

Packed moving bed internal diameter 47mm, height of bed 4500mm, D290 resin load volume 7.8L, the absorption feed liquid is the Na after thioated pre-treatment and dilution ₂WO ₄Solution contains WO ₃42.5g/L, Mo 0.64g/L, going into the post flow is 10L/h, reaches after the adsorption equilibrium, outlet sample analytical results is WO ₃42.2g/L, Mo 0.00080g/L, Mo/WO ₃=1.88 * 10 ^-5

Fluidized-bed height of bed 2000mm, bed inner major diameter 47mm, the saturated molybdenum resin of every batch processing 1L, fresh parsing agent composition is NaClO 0.8mol/L, NaOH 0.4mol/L, regenerator is for containing Cl ^-106.5g/L NaCl solution, the desorbed solution temperature out is the highest 52 ℃.

Embodiment 2

Packed moving bed that uses and sulfuration bed are identical with embodiment 1, and polymeric adsorbent and dress column volume are too.The absorption stock liquid is through it (NH of thioated pre-treatment ₄) ₂WO ₄Solution, its composition are WO ₃118.5g/L, Mo 0.56g/L, absorption feed liquor flow velocity 4.8L/h reaches after the adsorption equilibrium, and every 2h gets a sample, and its serial sampling analytical results is shown in table 1.

Table 1 removes molybdenum liquid composition analysis result

Test piece number (Test pc No.) WO ₃Concentration g/L Mo concentration g/L Mo/WO ₃* 10 ^-5

1 111 0.005 4.5

2 119 0.006 5.0

3 119 0.005 4.2

4 119 0.008 6.7

5 119 0.004 3.4

Parsing, regenerative process and parameter be with embodiment 1,54 ℃ of the highest temperature outs of desorbed solution, and regenerator is an ammonium chloride solution.

Claims

1. from tungstate solution, remove the method for molybdenum, it is characterized in that:

Adopt packed moving bed and fluidized-bed ion exchange technique to remove molybdenum,

The absorption molybdenum carries out object solution in packed moving bed (1)---and the thioated feed liquid enters continuously from the cylinder bottom, by being duration of contact 20～100min control feed liquor speed, removes molybdenum liquid and overflows from the resin bed top; The resin of saturated load molybdenum is regularly emitted from the cylinder bottom in batches, and the regenerating resin of same amount adds from the cylinder top simultaneously; Every batch of discharging amount of saturated resin is 1/8～1/10 of the total loading capacity of resin; Meanwhile, resin after the regeneration of the additional equal amts in column top is to keep the former height of resin bed; The every batch of resin is emitted and by resin the saturated adsorption capacity of molybdenum and unit time is advanced post molybdenum amount pitch time and calculate and determine;

Resolve molybdenum and regeneration of resin and in fluidized-bed (2), carry out, the tungsten that flush away is carried secretly behind the resin input fluidized-bed of saturated load molybdenum, washings returns batching; Resolve molybdenum with the sodium hypochlorite solution alkaline again; Resolve operation from the bottom feed liquor, the top fluid, feed liquor speed can suspend with resin or fluidised form turns to principle; Resolve agent NaClO concentration 0.4～1.0mol/L, the outlet liquid temp is controlled at below 60 ℃ during parsing; Using regenerator process resin, regenerator after molybdenum is resolved is the chloride solution that contains Cl-80～120g/L, and the resin through resolving regeneration has recovered the resinogen color and luster, and loading capacity is stable, returns absorption next time.

2. the method for removing molybdenum from tungstate solution according to claim 1 is characterized in that: object solution comprises sodium tungstate solution and ammonium tungstate solution, its feed liquor WO for through the pretreated tungstate solution of thioated ₃Concentration is ammonium tungstate solution 100～300g/L, sodium tungstate solution 20～200g/L.

3. the method for removing molybdenum from tungstate solution according to claim 1, it is characterized in that: ion exchange resin is anionite-exchange resin, comprises macroporous type and gel type strong base and weak base anion-exchange resin.