Nothing Special   »   [go: up one dir, main page]

CN114917757A - Preparation system of high solubility ammonium metatungstate - Google Patents

Preparation system of high solubility ammonium metatungstate Download PDF

Info

Publication number
CN114917757A
CN114917757A CN202210664346.6A CN202210664346A CN114917757A CN 114917757 A CN114917757 A CN 114917757A CN 202210664346 A CN202210664346 A CN 202210664346A CN 114917757 A CN114917757 A CN 114917757A
Authority
CN
China
Prior art keywords
solution
ammonium metatungstate
specifically
prepare
ammonium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202210664346.6A
Other languages
Chinese (zh)
Inventor
谢海龙
谭平
罗香东
张廷安
王桂英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ganzhou Haisheng Tungsten Industry Co ltd
Original Assignee
Ganzhou Haisheng Tungsten Industry Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ganzhou Haisheng Tungsten Industry Co ltd filed Critical Ganzhou Haisheng Tungsten Industry Co ltd
Priority to CN202210664346.6A priority Critical patent/CN114917757A/en
Publication of CN114917757A publication Critical patent/CN114917757A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B01D1/16—Evaporating by spraying
    • B01D1/18—Evaporating by spraying to obtain dry solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J6/00—Heat treatments such as Calcining; Fusing ; Pyrolysis
    • B01J6/001—Calcining
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/36—Hydrophilic membranes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a preparation system of high-solubility ammonium metatungstate, relating to the technical field of ammonium metatungstate preparation and comprising the following steps: the pyrolysis device is used for heating and calcining the ammonium paratungstate to prepare a decomposed material; the leaching device is used for adjusting the pH of the decomposed material impregnation liquid to 2-4 to prepare an ammonium metatungstate solution; a nanofiltration membrane is arranged in the filtering device and is used for intercepting and filtering divalent salt in the ammonium metatungstate solution to obtain filtrate; the concentration device is used for concentrating the filtrate to obtain a concentrated solution; and the spray drying device is used for carrying out spray drying on the concentrated solution to prepare the ammonium metatungstate powder. According to the invention, ammonium paratungstate is converted into ammonium metatungstate by using a divalent acid solution, and then the ammonium paratungstate is removed by combining the characteristic of high interception rate of a nanofiltration membrane on divalent ions, so that the ammonium metatungstate with high purity and high solubility is prepared.

Description

Preparation system of high solubility ammonium metatungstate
Technical Field
The invention relates to the technical field of preparation of ammonium metatungstate, in particular to a preparation system of high-solubility ammonium metatungstate.
Background
Ammonium Metatungstate (AMT) is an important compound product in the smelting process, has wide application range, is a raw material for preparing capacitors, nuclear shields, flame retardants and alkaline corrosion agents, and is also an excellent raw material for superfine tungsten powder, high-specific-gravity alloy tungsten powder, phosphorus tungsten powder, arsenic tungsten powder and silicon tungsten powder.
Chinese patent publication No. CN106395906A discloses a method and system for preparing ammonium metatungstate from tungsten oxide waste, which adopts a process of twice leaching with nitric acid, and then concentrating and drying to obtain sodium metatungstate. In the patent, a nitric acid twice impregnation process is adopted, so that nitrate is difficult to remove at the later stage, and the purity of ammonium metatungstate is not high.
Disclosure of Invention
The invention aims to solve at least one technical problem in the prior art and provides a preparation system of high-solubility ammonium metatungstate.
The technical solution of the invention is as follows:
a preparation system of high-solubility ammonium metatungstate comprises:
the pyrolysis device is used for heating and calcining the ammonium paratungstate to prepare a decomposed material;
the leaching device is used for adjusting the pH of the decomposed material impregnation liquid to 2-4 to prepare an ammonium metatungstate solution;
a nanofiltration membrane is arranged in the filtering device and is used for intercepting and filtering divalent salt in the ammonium metatungstate solution to obtain filtrate;
the concentration device is used for concentrating the filtrate to obtain a concentrated solution;
and the spray drying device is used for carrying out spray drying on the concentrated solution to prepare the ammonium metatungstate powder.
In a preferred embodiment of the present invention, the divalent acid solution is sulfuric acid.
As the scheme of the invention, the preparation method of the nanofiltration membrane comprises the following steps: soaking the polysulfone base membrane in the first solution and the second solution for a period of time in sequence, and performing heat treatment after the soaking is finished to obtain the polysulfone base membrane;
wherein the first solution is specifically: dissolving PIP monomer in water;
the second solution is specifically: dissolving TMC monomer in n-hexane, continuously adding inorganic nanoparticles, and mixing uniformly.
As a preferable scheme of the invention, the heat treatment is specifically at 70-90 ℃ for 7-15 min.
In a preferred embodiment of the present invention, a hydrophilic polymer is further added to the first solution.
In a preferred embodiment of the present invention, the inorganic nanoparticles are at least one of alumina, silica, and titania.
In a preferred embodiment of the present invention, the dipping is carried out by ultrasonic treatment.
In a preferred embodiment of the present invention, the inorganic nanoparticles are present in an amount of 0.005 to 0.1 (w/v)% based on the second solution.
The invention has the beneficial effects that:
(1) according to the preparation system of the high-solubility ammonium tungstate, ammonium paratungstate is converted into ammonium metatungstate by using the divalent acid solution, and the ammonium paratungstate is removed by combining the characteristic of high interception rate of the nanofiltration membrane on divalent ions, so that the high-purity high-solubility ammonium metatungstate is prepared.
(2) According to the preparation system of the high-solubility ammonium tungstate, the inorganic nano particles are added into the organic phase of the second solution, and the stability of the organic phase is better than that of the aqueous phase added into the first solution, so that the interception rate of the nanofiltration membrane on divalent salt is higher.
(3) According to the preparation system of the high-solubility ammonium tungstate, the hydrophilic polymer is added into the first solution and is embedded into the active layer of the nanofiltration membrane through interfacial polymerization, so that the hydrophilicity of the nanofiltration membrane is improved, and the water flux is increased.
Drawings
FIG. 1 is a schematic structural diagram of a preferred embodiment of the present invention;
in the figure, 100-pyrolysis unit, 200-leaching unit, 300-filtering unit, 400-concentrating unit, 500-spray drying unit.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
It should be noted that: TMC is trimesoyl chloride, PIP is piperazine.
Example 1
A preparation system of high-solubility ammonium metatungstate comprises:
the pyrolysis device 100, specifically a rotary kiln, is used for heating and calcining ammonium paratungstate at a calcination temperature of 230 ℃ to obtain a decomposed material;
the leaching device 200, which may be a reaction kettle, is used for placing a divalent acid solution, specifically a 12 wt% sulfuric acid solution, and is used for adding a decomposition material into the divalent acid solution, and controlling the pH to be 3 to prepare an ammonium metatungstate solution;
the filtering device 300, which can be specifically a filtering tank, is provided with a nanofiltration membrane, the liquid passing pressure of the nanofiltration membrane is 0.06Mpa, and the filtering device is used for intercepting and filtering divalent salt in the ammonium metatungstate solution to obtain filtrate;
the concentration device 400, which may be a concentration kettle specifically, is configured to concentrate the filtrate to obtain a concentrated solution when the specific gravity reaches 1.7;
and the spray drying device 500 is used for carrying out spray drying on the concentrated solution to prepare ammonium metatungstate powder.
The preparation method of the nanofiltration membrane comprises the following steps: soaking the polysulfone base membrane in the first solution and the second solution for a period of time in sequence, and performing heat treatment after the soaking is finished to obtain the polysulfone base membrane; and carrying out ultrasonic treatment during the impregnation.
Wherein the first solution is specifically: dissolving PIP monomer in water to prepare PIP solution with the concentration of 1 (w/v)%;
the second solution is specifically: dissolving TMC monomer in n-hexane to obtain TMC solution with concentration of 0.15 (w/v)%, adding inorganic nanoparticles, and mixing. The inorganic nanoparticles accounted for 0.009 (w/v)% of the second solution.
The heat treatment is specifically carried out at 85 ℃ for 12 min.
The first solution is also added with hydrophilic polymer which accounts for 0.06 wt% of the mass of the first solution, and the hydrophilic polymer is sodium polyvinylbenzene sulfonate.
The inorganic nanoparticles are titanium dioxide.
Example 2
A preparation system of high-solubility ammonium metatungstate comprises:
the pyrolysis device 100, specifically a rotary kiln, is used for heating and calcining ammonium paratungstate at a calcination temperature of 230 ℃ to obtain a decomposed material;
the leaching device 200, which may be a reaction kettle, is used for placing a divalent acid solution, specifically a 12 wt% sulfuric acid solution, and is used for adding a decomposition material into the divalent acid solution, and controlling the pH value to be 2-4 to prepare an ammonium metatungstate solution;
the filtering device 300, which can be specifically a filtering tank, is provided with a nanofiltration membrane, the liquid passing pressure of the nanofiltration membrane is 0.06Mpa, and the filtering device is used for intercepting and filtering divalent salt in the ammonium metatungstate solution to obtain filtrate;
the concentration device 400, which may be a concentration kettle, is used for concentrating the filtrate to obtain a concentrated solution when the specific gravity reaches 1.6-1.8;
and the spray drying device 500 is used for carrying out spray drying on the concentrated solution to prepare ammonium metatungstate powder.
The preparation method of the nanofiltration membrane comprises the following steps: soaking the polysulfone base membrane in the first solution and the second solution for a period of time in sequence, and performing heat treatment after the soaking is finished to obtain the polysulfone base membrane; and carrying out ultrasonic treatment during the impregnation.
Wherein the first solution is specifically: dissolving PIP monomer in water to prepare PIP solution with the concentration of 1 (w/v)%;
the second solution is specifically: dissolving TMC monomer in n-hexane to obtain TMC solution with concentration of 0.15 (w/v)%, adding inorganic nanoparticles, and mixing. The inorganic nanoparticles comprise 0.02 (w/v)% of the second solution.
The heat treatment is specifically carried out at 80 ℃ for 11 min.
The first solution is also added with hydrophilic polymer which accounts for 0.09 wt% of the mass of the first solution, and the hydrophilic polymer is sodium polystyrene sulfonate.
The inorganic nanoparticles are alumina.
Example 3
A preparation system of high-solubility ammonium metatungstate comprises:
the pyrolysis device 100, specifically a rotary kiln, is used for heating and calcining ammonium paratungstate at a calcination temperature of 230 ℃ to obtain a decomposed material;
the leaching device 200, which may be a reaction kettle, is used for placing a divalent acid solution, specifically a 15 wt% sulfuric acid solution, and is used for adding a decomposition material into the divalent acid solution, and controlling the pH to be 4 to prepare an ammonium metatungstate solution;
the filtering device 300, which can be specifically a filtering tank, is provided with a nanofiltration membrane, the liquid passing pressure of the nanofiltration membrane is 0.06Mpa, and the filtering device is used for intercepting and filtering divalent salt in the ammonium metatungstate solution to obtain filtrate;
the concentration device 400, which may be a concentration kettle specifically, is configured to concentrate the filtrate, and when the specific gravity reaches 1.8, a concentrated solution is prepared;
and the spray drying device 500 is used for carrying out spray drying on the concentrated solution to prepare ammonium metatungstate powder.
The preparation method of the nanofiltration membrane comprises the following steps: soaking the polysulfone base membrane in the first solution and the second solution for a period of time in sequence, and performing heat treatment after the soaking is finished to obtain the polysulfone base membrane; and carrying out ultrasonic treatment during the impregnation.
Wherein the first solution is specifically: dissolving PIP monomer in water to prepare PIP solution with the concentration of 1 (w/v)%;
the second solution is specifically: dissolving TMC monomer in n-hexane to obtain TMC solution with concentration of 0.15 (w/v)%, adding inorganic nanoparticles, and mixing. The inorganic nanoparticles comprise 0.01 (w/v)% of the second solution.
The heat treatment is specifically carried out at 70 ℃ for 15 min.
The first solution is also added with hydrophilic polymer which accounts for 0.8 wt% of the mass of the first solution, specifically sodium polystyrene sulfonate.
The inorganic nanoparticles are titanium dioxide.
Example 4
A preparation system of high-solubility ammonium metatungstate comprises:
the pyrolysis device 100, specifically a rotary kiln, is used for heating and calcining ammonium paratungstate at a calcination temperature of 230 ℃ to obtain a decomposed material;
the leaching device 200, which may be a reaction kettle, is used for placing a divalent acid solution, specifically a 10 wt% sulfuric acid solution, and is used for adding a decomposition material into the divalent acid solution, controlling the pH to be 3, and preparing an ammonium metatungstate solution;
the filtering device 300, which can be specifically a filtering tank, is provided with a nanofiltration membrane, the liquid passing pressure of the nanofiltration membrane is 0.06Mpa, and the filtering device is used for intercepting and filtering divalent salt in the ammonium metatungstate solution to obtain filtrate;
the concentration device 400, which may be a concentration kettle specifically, is configured to concentrate the filtrate to obtain a concentrated solution when the specific gravity reaches 1.7;
and the spray drying device 500 is used for carrying out spray drying on the concentrated solution to prepare ammonium metatungstate powder.
The preparation method of the nanofiltration membrane comprises the following steps: soaking the polysulfone base membrane in the first solution and the second solution for a period of time in sequence, and performing heat treatment after the soaking is finished to obtain the polysulfone base membrane; and carrying out ultrasonic treatment during the impregnation.
Wherein the first solution is specifically: dissolving PIP monomer in water to prepare PIP solution with the concentration of 1 (w/v)%;
the second solution is specifically: dissolving TMC monomer in n-hexane to obtain TMC solution with concentration of 0.15 (w/v)%, adding inorganic nanoparticles, and mixing. The inorganic nanoparticles comprise 0.008 (w/v)% of the second solution.
The heat treatment is specifically treatment at 80 ℃ for 10 min.
The first solution is also added with hydrophilic polymer which accounts for 0.06 wt% of the mass of the first solution, and the hydrophilic polymer is sodium polyvinylbenzene sulfonate.
The inorganic nanoparticles are silica.
Example 5
A preparation system of high-solubility ammonium metatungstate comprises:
the pyrolysis device 100, specifically a rotary kiln, is used for heating and calcining ammonium paratungstate at a calcination temperature of 230 ℃ to obtain a decomposed material;
the leaching device 200, which may be a reaction kettle, is used for adding a divalent acid solution, specifically a 12 wt% sulfuric acid solution, to the divalent acid solution, and controlling the pH to 2 to obtain an ammonium metatungstate solution;
the filtering device 300, which can be specifically a filtering tank, is provided with a nanofiltration membrane, the liquid passing pressure of the nanofiltration membrane is 0.06Mpa, and the filtering device is used for intercepting and filtering divalent salt in the ammonium metatungstate solution to obtain filtrate;
the concentration device 400, which may be a concentration kettle specifically, is configured to concentrate the filtrate, and when the specific gravity reaches 1.6, a concentrated solution is prepared;
and the spray drying device 500 is used for carrying out spray drying on the concentrated solution to prepare ammonium metatungstate powder.
The preparation method of the nanofiltration membrane comprises the following steps: soaking the polysulfone base membrane in the first solution and the second solution for a period of time in sequence, and performing heat treatment after the soaking is finished to obtain the polysulfone base membrane; and carrying out ultrasonic treatment during the impregnation.
Wherein the first solution is specifically: dissolving PIP monomer in water to prepare PIP solution with the concentration of 1 (w/v)%;
the second solution is specifically: dissolving TMC monomer in n-hexane to obtain TMC solution with concentration of 0.15 (w/v)%, adding inorganic nanoparticles, and mixing. The inorganic nanoparticles comprise 0.005 (w/v)% of the second solution.
The heat treatment is specifically carried out at 90 ℃ for 7 min.
The first solution is also added with hydrophilic polymer which accounts for 0.05 wt% of the mass of the first solution, and specifically is sodium polystyrene sulfonate.
The inorganic nanoparticles are alumina.
Comparative example 1 (monovalent acid)
A preparation system of high-solubility ammonium metatungstate comprises:
the pyrolysis device 100, specifically a rotary kiln, is used for heating and calcining ammonium paratungstate at a calcination temperature of 230 ℃ to obtain a decomposed material;
the leaching device 200, which may be a reaction kettle, is used for placing monovalent acid solution, specifically 12 wt% nitric acid solution, and is used for adding the decomposed material into the monovalent acid solution, controlling the pH value to be 3, and preparing ammonium metatungstate solution;
the filtering device 300, which can be specifically a filtering tank, is provided with a nanofiltration membrane, the liquid passing pressure of the nanofiltration membrane is 0.06Mpa, and the filtering device is used for intercepting and filtering divalent salt in the ammonium metatungstate solution to obtain filtrate;
the concentration device 400, which may be a concentration kettle specifically, is configured to concentrate the filtrate to obtain a concentrated solution when the specific gravity reaches 1.7;
and the spray drying device 500 is used for carrying out spray drying on the concentrated solution to prepare ammonium metatungstate powder.
The preparation method of the nanofiltration membrane comprises the following steps: soaking the polysulfone base membrane in the first solution and the second solution for a period of time in sequence, and performing heat treatment after the soaking is finished to obtain the polysulfone base membrane; and carrying out ultrasonic treatment during the impregnation.
Wherein the first solution is specifically: dissolving PIP monomer in water to prepare PIP solution with the concentration of 1 (w/v)%;
the second solution is specifically: dissolving TMC monomer in n-hexane to obtain TMC solution with concentration of 0.15 (w/v)%, adding inorganic nanoparticles, and mixing. The inorganic nanoparticles accounted for 0.009 (w/v)% of the second solution.
The heat treatment is specifically carried out at 85 ℃ for 12 min.
The first solution is also added with hydrophilic polymer which accounts for 0.06 wt% of the mass of the first solution, and specifically is sodium polystyrene sulfonate.
The inorganic nanoparticles are titanium dioxide.
Comparative example 2 (inorganic nanoparticles added to the first solution)
A preparation system of high-solubility ammonium metatungstate comprises:
the pyrolysis device 100, specifically a rotary kiln, is used for heating and calcining ammonium paratungstate at a calcination temperature of 230 ℃ to obtain a decomposed material;
the leaching device 200, which may be a reaction kettle, is used for adding a divalent acid solution, specifically a 12 wt% sulfuric acid solution, to the divalent acid solution, and controlling the pH to 3 to prepare an ammonium metatungstate solution;
the filtering device 300, which can be specifically a filtering tank, is provided with a nanofiltration membrane, the liquid passing pressure of the nanofiltration membrane is 0.06Mpa, and the filtering device is used for intercepting and filtering divalent salt in the ammonium metatungstate solution to obtain filtrate;
the concentration device 400, which may be a concentration kettle specifically, is configured to concentrate the filtrate to obtain a concentrated solution when the specific gravity reaches 1.7;
and the spray drying device 500 is used for carrying out spray drying on the concentrated solution to prepare ammonium metatungstate powder.
The preparation method of the nanofiltration membrane comprises the following steps: soaking the polysulfone base membrane in the first solution and the second solution for a period of time in sequence, and performing heat treatment after the soaking is finished to obtain the polysulfone base membrane; and carrying out ultrasonic treatment during the impregnation.
Wherein the first solution is specifically: dissolving PIP monomer in water to prepare PIP solution with the concentration of 1 (w/v)%; continuously adding the inorganic nano particles and uniformly mixing. The inorganic nanoparticles account for 0.009 (w/v)% of the first solvent.
The second solution is specifically: TMC monomer was dissolved in n-hexane to prepare a 0.15 (w/v)% TMC solution.
The heat treatment is specifically carried out at 85 ℃ for 12 min.
The first solution is also added with hydrophilic polymer which accounts for 0.06 wt% of the mass of the first solution, and the hydrophilic polymer is sodium polyvinylbenzene sulfonate.
The inorganic nanoparticles are titanium dioxide.
Comparative example 3 (hydrophilic polymer was not added to the first solution)
A preparation system of high-solubility ammonium metatungstate comprises:
the pyrolysis device 100, specifically a rotary kiln, is used for heating and calcining ammonium paratungstate at a calcination temperature of 230 ℃ to obtain a decomposed material;
the leaching device 200, which may be a reaction kettle, is used for adding a divalent acid solution, specifically a 12 wt% sulfuric acid solution, to the divalent acid solution, and controlling the pH to 3 to prepare an ammonium metatungstate solution;
the filtering device 300, which can be specifically a filtering tank, is provided with a nanofiltration membrane, the liquid passing pressure of the nanofiltration membrane is 0.06Mpa, and the filtering device is used for intercepting and filtering divalent salt in the ammonium metatungstate solution to obtain filtrate;
the concentration device 400, which may be a concentration kettle specifically, is configured to concentrate the filtrate to obtain a concentrated solution when the specific gravity reaches 1.7;
and the spray drying device 500 is used for carrying out spray drying on the concentrated solution to prepare ammonium metatungstate powder.
The preparation method of the nanofiltration membrane comprises the following steps: soaking the polysulfone base membrane in the first solution and the second solution for a period of time in sequence, and performing heat treatment after the soaking is finished to obtain the polysulfone base membrane; and carrying out ultrasonic treatment during the impregnation.
Wherein the first solution is specifically: dissolving PIP monomer in water to prepare PIP solution with the concentration of 1 (w/v)%;
the second solution is specifically: dissolving TMC monomer in n-hexane to obtain TMC solution with concentration of 0.15 (w/v)%, adding inorganic nanoparticles, and mixing. The inorganic nanoparticles comprise 0.009 (w/v)% of the second solution.
The heat treatment is specifically carried out at 85 ℃ for 12 min.
The inorganic nanoparticles are titanium dioxide.
The ammonium metatungstate products of the above examples and comparative examples were subjected to purity tests, and the test values are shown in the following table.
Test specimen Purity (in WO) 3 Meter, unit wt%)
Example 1 97.1
Example 2 97.3
Example 3 97.8
Example 4 97.9
Example 5 97.6
Comparative example 1 91.1
Comparative example 2 94.6
Comparative example 3 92.3
As can be seen from table 1, the example is higher in purity than the comparative example, the main reasons for this may be as follows: the analysis of the comparative example 1 shows that the divalent acid and the nanofiltration membrane are combined in the example, so that the interception rate of divalent sulfate is higher, and the purity of the product is better; the analysis of comparative example 2 shows that the example has better stability compared with the case of adding inorganic nanoparticles into the organic phase of the second solution and the aqueous phase of the first solution, so that the interception rate of the divalent salt by the nanofiltration membrane is higher. The analysis of comparative example 3 shows that in the examples, the hydrophilic polymer is added to the first solution and is embedded in the active layer of the nanofiltration membrane by interfacial polymerization, thereby improving the hydrophilicity of the nanofiltration membrane and increasing the water flux.
The above additional technical features can be freely combined and used in addition by those skilled in the art without conflict.
The above description is only a preferred embodiment of the present invention, and the technical solutions that achieve the objects of the present invention by substantially the same means are within the protection scope of the present invention.

Claims (8)

1. The utility model provides a preparation system of high solubility ammonium metatungstate which characterized in that includes:
the pyrolysis device (100) is used for heating and calcining the ammonium paratungstate to prepare a decomposed material;
a leaching device (200) in which a divalent acid solution is placed, the leaching device being configured to adjust the pH of the decomposed material impregnation solution to 2-4 to produce an ammonium metatungstate solution;
a filter device (300) which is internally provided with a nanofiltration membrane and is used for intercepting and filtering divalent salt in the ammonium metatungstate solution and taking filtrate;
the concentration device (400) is used for concentrating the filtrate to obtain a concentrated solution;
and the spray drying device (500) is used for carrying out spray drying on the concentrated solution to prepare ammonium metatungstate powder.
2. The system of claim 1, wherein the divalent acid solution is sulfuric acid.
3. The system for preparing the high-solubility ammonium metatungstate according to claim 1, wherein the nanofiltration membrane is prepared by the following steps: soaking the polysulfone base membrane in the first solution and the second solution for a period of time in sequence, and performing heat treatment after the soaking is finished to obtain the polysulfone base membrane;
wherein the first solution is specifically: dissolving PIP monomer in water;
the second solution is specifically: dissolving TMC monomer in n-hexane, continuously adding inorganic nanoparticles, and mixing uniformly.
4. The system for preparing high-solubility ammonium metatungstate according to claim 3, wherein the heat treatment is carried out at 70-90 ℃ for 7-15 min.
5. The system of claim 3, wherein a hydrophilic polymer is further added to the first solution.
6. The system of claim 3, wherein the inorganic nanoparticles are at least one of alumina, silica, and titania.
7. The system for preparing high-solubility ammonium metatungstate according to claim 3, wherein ultrasonic treatment is performed during the impregnation.
8. The system of claim 3, wherein the inorganic nanoparticles comprise 0.005-0.1 (w/v)% of the second solution.
CN202210664346.6A 2022-06-13 2022-06-13 Preparation system of high solubility ammonium metatungstate Pending CN114917757A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210664346.6A CN114917757A (en) 2022-06-13 2022-06-13 Preparation system of high solubility ammonium metatungstate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210664346.6A CN114917757A (en) 2022-06-13 2022-06-13 Preparation system of high solubility ammonium metatungstate

Publications (1)

Publication Number Publication Date
CN114917757A true CN114917757A (en) 2022-08-19

Family

ID=82814892

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210664346.6A Pending CN114917757A (en) 2022-06-13 2022-06-13 Preparation system of high solubility ammonium metatungstate

Country Status (1)

Country Link
CN (1) CN114917757A (en)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1923347A (en) * 2006-09-01 2007-03-07 哈尔滨工业大学 Aluminium oxide granule/fragrant polyamide blending isolation film and preparation process thereof
CN101912741A (en) * 2010-08-05 2010-12-15 贵阳时代沃顿科技有限公司 Polyamide composite reverse osmosis membrane containing nano materials
CN102942222A (en) * 2012-10-28 2013-02-27 孙世凡 Method for preparing ammonium tungstate by treating waste tungsten oxide
CN103877872A (en) * 2014-03-28 2014-06-25 杭州水处理技术研究开发中心有限公司 Preparation method of nano material modified poly piperazine amide nanofiltration membrane
CN104667759A (en) * 2013-11-29 2015-06-03 贵阳时代沃顿科技有限公司 Preparation method of high-throughput anti-pollution composite nanofiltration membrane
CN105018754A (en) * 2014-04-17 2015-11-04 上海凯鑫分离技术有限公司 Extraction technology of ion-absorbed rare earth mine
CN106636632A (en) * 2016-09-27 2017-05-10 中南大学 Method for conducting normal-pressure decomposition on wolframite or scheelite and wolframite mixture ores in alkali system
CN106823842A (en) * 2017-03-28 2017-06-13 天津大学 A kind of preparation method of graphene oxide composite nano filter membrane
CN108439472A (en) * 2018-05-08 2018-08-24 江西铜鼓有色冶金化工有限责任公司 A kind of method and system preparing the ammonium metatungstate for petroleum cracking catalyst
CN210915348U (en) * 2019-10-23 2020-07-03 江西铜鼓有色冶金化工有限责任公司 A preparation system for ammonium metatungstate of denitration catalyst
CN113117527A (en) * 2021-05-14 2021-07-16 万华化学集团股份有限公司 Nanofiltration membrane and preparation method and application thereof
CN216694345U (en) * 2021-11-17 2022-06-07 赣州海盛钨业股份有限公司 Precipitation drying device is used in production of yellow tungsten oxide

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1923347A (en) * 2006-09-01 2007-03-07 哈尔滨工业大学 Aluminium oxide granule/fragrant polyamide blending isolation film and preparation process thereof
CN101912741A (en) * 2010-08-05 2010-12-15 贵阳时代沃顿科技有限公司 Polyamide composite reverse osmosis membrane containing nano materials
CN102942222A (en) * 2012-10-28 2013-02-27 孙世凡 Method for preparing ammonium tungstate by treating waste tungsten oxide
CN104667759A (en) * 2013-11-29 2015-06-03 贵阳时代沃顿科技有限公司 Preparation method of high-throughput anti-pollution composite nanofiltration membrane
CN103877872A (en) * 2014-03-28 2014-06-25 杭州水处理技术研究开发中心有限公司 Preparation method of nano material modified poly piperazine amide nanofiltration membrane
CN105018754A (en) * 2014-04-17 2015-11-04 上海凯鑫分离技术有限公司 Extraction technology of ion-absorbed rare earth mine
CN106636632A (en) * 2016-09-27 2017-05-10 中南大学 Method for conducting normal-pressure decomposition on wolframite or scheelite and wolframite mixture ores in alkali system
CN106823842A (en) * 2017-03-28 2017-06-13 天津大学 A kind of preparation method of graphene oxide composite nano filter membrane
CN108439472A (en) * 2018-05-08 2018-08-24 江西铜鼓有色冶金化工有限责任公司 A kind of method and system preparing the ammonium metatungstate for petroleum cracking catalyst
CN210915348U (en) * 2019-10-23 2020-07-03 江西铜鼓有色冶金化工有限责任公司 A preparation system for ammonium metatungstate of denitration catalyst
CN113117527A (en) * 2021-05-14 2021-07-16 万华化学集团股份有限公司 Nanofiltration membrane and preparation method and application thereof
CN216694345U (en) * 2021-11-17 2022-06-07 赣州海盛钨业股份有限公司 Precipitation drying device is used in production of yellow tungsten oxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘久清: "纳滤膜分离技术处理APT结晶母液及制备偏钨酸铵的研究", 《中国硕士学位论文全文数据库（工程科技Ⅰ辑）》, no. 2, 15 February 2002 (2002-02-15), pages 012 - 25 *
黄伯云: "《自然地理与资源环境专业实验教程》", 哈尔滨工程大学出版社, pages: 281 - 282 *

Similar Documents

Publication Publication Date Title
RU2701564C1 (en) Method of producing ammonium polyvanadate from a high-concentration vanadium-containing solution
CN102828037B (en) Method of preparing low-silicon low-phosphorus potassium metavanadate solution from vanadium slag
CN110280144B (en) Preparation method of aluminum oxide/graphene oxide/polyvinyl alcohol composite nanofiltration membrane
CN111994952A (en) Method for preparing high-purity vanadium pentoxide by vacuum sublimation of metallurgical-grade vanadium pentoxide
WO2010004925A1 (en) Method of recovering silicon, titanium, and fluorine
CN108754186A (en) The method for preparing vfanadium compound containing vanadium solution
JP5774619B2 (en) Production of low BET trimanganese tetraoxide and particle size control method, and trimanganese tetraoxide
CN113816428A (en) Process for preparing ammonium paratungstate
CN103626230B (en) Method for preparing vanadyl sulfate
CN113336258A (en) Method for preparing active copper oxide from sponge copper
CN111446478B (en) Method for preparing vanadium battery electrolyte by taking vanadium-rich liquid as raw material
CN102828036B (en) Method of preparing potassium metavanadate solution from vanadium slag
CN114917757A (en) Preparation system of high solubility ammonium metatungstate
CN105214644B (en) Modified titanium and its preparation method and application
CN114768780A (en) Preparation method and application of Zn-Fe Prussian blue analogue composite material
CN115747525A (en) Purification method of crude vanadium and application thereof
TWI548451B (en) Recycling method of discarded denitrification catalyst
CN110438349B (en) Method for preparing high-purity ammonium molybdate from low-grade molybdenum material
CN212450666U (en) Preparation system of high solubility ammonium metatungstate
CN109183093B (en) Preparation method of tetraammine palladium bicarbonate compound
CN107899430A (en) A kind of processing method of nitrogen-containing wastewater
CN109385641B (en) Method for preparing ammonium polyvanadate by electrolyzing sodium vanadate solution
CN112871148A (en) Preparation method of zirconium dioxide carrier for noble metal catalyst
CN107032385B (en) Method for preparing basic copper nitrate superfine powder by microwave hydrothermal method
CN111039448A (en) Method for removing manganese impurities in acidic solution by ozone

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination