Ammonium Paratungstate Hydrate Crystallization via Continuous Re-extraction

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Solution Overview

Problem

Current processes for producing ammonium paratungstate hydrates and decahydrate suffer from low bulk density, high impurity levels, high energy consumption, and high process costs, with previous methods resulting in finely crystalline products that are difficult to purify and have low crystallization yields.

Innovation Solution

A continuous process involving re-extraction of a tungsten-loaded organic phase with an aqueous ammonia solution in a mixer-settler device, optimizing the NH3:W molar ratio, phase volume ratios, and stirring conditions to achieve direct crystallization of coarsely crystalline, highly pure ammonium paratungstate hydrate with high bulk density.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If conventional evaporation crystallization is used to produce ammonium paratungstate, then the process is simple, but the product has low bulk density (0.7-1.03 g/cm³) and fine crystalline morphology

Engineering Contradiction:
Improveprocess simplicityVSAvoidcrystal size and bulk density
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The invention changes the crystallization parameters by controlling pH (7.0-7.4), temperature (0-25°C), and ammonia-to-tungsten molar ratio (3.6:1 to 50.1:1) during re-extraction to produce coarse crystals with bulk density of 1.7-2.1 g/cm³, resolving the contradiction between process simplicity and product quality

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention implements continuous re-extraction followed by continuous crystallization in a controlled environment, maintaining optimal conditions throughout the process to consistently produce high-density coarse crystals without interrupting the production flow

Inventive Principle:
Principle #20Continuity of useful action

2Manufacturing precision

If liquid-liquid extraction with amine-containing organic phases is used to purify tungsten, then impurity removal is effective, but APW x 10H2O formation deteriorates phase separation and product purity

Engineering Contradiction:
Improveimpurity removal efficiencyVSAvoidphase separation quality
Core Design Contradiction:
Manufacturing precisionVSReliability

Solution Approach 1:

The invention performs preliminary re-extraction of tungsten from the organic phase with ammonia solution to form ammonium tungstate, converting the tungsten into a form that precipitates as coarse APW crystals, thereby preventing the formation of fine APW x 10H2O crystals that would interfere with phase separation

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The invention changes the chemical form of tungsten through controlled re-extraction and crystallization at specific pH and temperature conditions, transforming it from a state that forms fine interfering crystals to a state that forms coarse, easily separable crystals

Inventive Principle:
Principle #35Parameter changes

3Quantity of substance

If re-extraction with high NH3:W molar ratio is used, then ammonium tungstate solution is formed, but crystallization yield is low (maximum 65%) and phase separation is slow

Engineering Contradiction:
Improveammonium tungstate formationVSAvoidcrystallization yield and phase separation speed
Core Design Contradiction:
Quantity of substanceVSProductivity

Solution Approach 1:

The invention optimizes the NH3:W molar ratio to a specific range (3.6:1 to 50.1:1) and controls pH (7.0-7.4) and temperature (0-25°C) to achieve both complete ammonium tungstate formation and high crystallization yield of coarse crystals with rapid phase separation

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The invention monitors and controls the crystallization process parameters to ensure optimal conditions are maintained, achieving high crystallization yield and fast phase separation through controlled precipitation of coarse crystals

Inventive Principle:
Principle #23Feedback

4Ease of manufacture

If conventional processes are used to produce ammonium paratungstate, then production is established, but energy consumption is high due to evaporation concentration

Engineering Contradiction:
Improveestablished production methodVSAvoidenergy consumption
Core Design Contradiction:
Ease of manufactureVSUse of energy by moving object

Solution Approach 1:

The invention implements continuous re-extraction and crystallization processes that eliminate the energy-intensive evaporation step, maintaining continuous operation to produce coarse APW crystals directly from solution

Inventive Principle:
Principle #20Continuity of useful action

Solution Approach 2:

The invention changes the production approach from evaporation-based concentration to controlled crystallization at ambient or low temperatures, dramatically reducing energy consumption while producing high-quality coarse crystals

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

This process yields highly pure, coarsely crystalline ammonium paratungstate with high bulk density and improved crystallization yield, reducing energy consumption and process complexity while minimizing ammonia usage and impurities.

Implementation Method 1

a liquid-liquid extraction is carried out using amine-containing organic phases

Methodology Applied
Scientific EffectLiquid-liquid extraction: Liquid-Liquid Extraction

Implementation Method 2

re-extracted by adding dropwise 5-29% NH3 solution

Methodology Applied
Scientific EffectRe-extraction: Liquid-Liquid Extraction

Implementation Method 3

The resulting APW product is finally filtered and dried

Methodology Applied
Scientific EffectPrecipitation: Precipitation

Implementation Method 4

APW x 10 H2O during slow evaporation of an ammonium tungstate solution made from WO3 and NH3 solution, emerges

Methodology Applied
Scientific EffectCrystallization: Crystallisation

Implementation Method 5

The purified solution is usually concentrated by evaporation, with APW ultimately crystallizing out

Methodology Applied
Scientific EffectEvaporation: Evaporation

Implementation Method 6

phase separation during re-extraction

Methodology Applied
Scientific EffectPhase separation: Density Gradient

Data Source

PatentEP2118017B1Method for producing ammonium paratungstate hydrates and ammonium paratungstate decahydrate
Publication Date: 2016.10.12 H C STARCK GMBH
  • EP2118017B1 patent drawingFigure 1~2
  • EP2118017B1 patent drawingFigure 3
  • EP2118017B1 patent drawingFigure 4

AI summary

A method for continuous production of ammonium paratungstate hydrates by back extraction of a tungsten-containing organic phase with an aqueous ammonia solution. It is possible to directly produce coarse crystalline ammonium paratungstate hydrates on back extraction by selection of suitable method parameters. The above crystallise in high purity and in high yield. The production method can be carried out in a simple and energy-efficient manner.