CN102259927A - Method for preparing high-purity ammonium tetramolybdate - Google Patents
Method for preparing high-purity ammonium tetramolybdate Download PDFInfo
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000012065 filter cake Substances 0.000 claims abstract description 93
- 238000002156 mixing Methods 0.000 claims abstract description 65
- 238000001914 filtration Methods 0.000 claims abstract description 33
- 239000007787 solid Substances 0.000 claims abstract description 30
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000009834 vaporization Methods 0.000 claims description 7
- 230000008016 vaporization Effects 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 5
- 230000001186 cumulative effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 8
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 3
- 235000011114 ammonium hydroxide Nutrition 0.000 abstract 3
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 230000008020 evaporation Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 47
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 12
- 229940010552 ammonium molybdate Drugs 0.000 description 12
- 235000018660 ammonium molybdate Nutrition 0.000 description 12
- 239000011609 ammonium molybdate Substances 0.000 description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 10
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 229910052776 Thorium Inorganic materials 0.000 description 5
- 229910052770 Uranium Inorganic materials 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- 230000008602 contraction Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- -1 mechanical workout Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000024241 parasitism Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing high-purity ammonium tetramolybdate, which comprises the following steps of: mixing pure water and concentrated nitric acid, heating, adding ammonium tetramolybdate serving as a raw material until solution is turbid, reacting with heating and stirring, naturally cooling, filtering, and washing a solid to obtain a filter cake 1; mixing the filter cake 1 and pure water, stirring, heating, filtering, and washing a solid to obtain a filter cake 2; adding pure water, mixing, heating, adding dilute hydrochloric acid to regulate pH, reacting with heating, filtering, and washing a solid to obtain a filter cake 3; adding pure water, mixing with concentrated ammonia water, filtering, regulating the density and pH of filtrate by using pure water and concentrated nitric acid, adding concentrated nitric acid to regulate the pH, filtering, and washing a solid to obtain a filter cake 4; adding pure water, mixing with concentrated ammonia water, filtering, performing evaporation crystallization under reduced pressure, and filtering to obtain a filter cake 5; adding pure water, mixing with concentrated ammonia water, regulating the density and pH of solution, heating, adding concentrated nitric acid to regulate the pH, filtering, and washing a solid to obtain a filter cake 6; and drying the filter cake 6 until water content is less than or equal to 1.0g/cm<3> to obtain the ammonium tetramolybdate with the purity of more than or equal to 99.998 percent. By the method, the content of impurities in the ammonium tetramolybdate serving as the raw material can be effectively reduced.
Description
Technical field
The present invention relates to a kind of preparation method of high purity ammonium tetramolybdate, specifically, relate to a kind of further impurity-removing method of ammonium molybdate, ammonium tetramolybdate purity 〉=99.998% after removal of impurities is handled.
Background technology
Molybdenum is a kind of have high boiling point and dystectic refractory metal, have good thermal conductivity and electroconductibility, low thermal expansivity, excellent abrasive and erosion resistance are widely used in fields such as space flight and aviation, electricity power, microelectronics, super large-scale integration original paper, biological medicine, mechanical workout, medicine equipment, illumination, glass and national defense construction.Ammonium molybdate is the primary raw materials of all kinds of alloys of preparation metal molybdenum powder and molybdenum, ammonium molybdate also is the important source material of the classes of compounds of preparation commercial catalysts, petroleum catalyst and molybdenum, and the content of element impurity such as K, W, U, Th, Fe and P directly affects the processing of molybdenum and the use properties of metal molybdenum goods in the ammonium molybdate.Along with continuous progress in science and technology, the Application Areas of molybdenum constantly enlarges, and this just constantly proposes harsher requirement to the foreign matter content in the ammonium molybdate, high-purity developing direction that changes into to each ammonium molybdate production firm of ammonium molybdate.Particularly impurity potassium (K) in the ammonium molybdate and tungsten (W) are owing to potassium easily shifts in the insulation diaphragm grid of super large-scale integration original paper, very big to the interlayer properties influence between metal-oxide semiconductor (MOS); Tungsten and molybdenum are in the same gang of the periodic table of chemical element, influenced by lanthanide contraction, and atomic radius is approaching, and physicochemical property are close, are in parasitism, bring a lot of difficulties to separation.In sum, and the restriction that is subjected to traditional technology and production practical situation, potassium and tungsten inclusion content in the ammonium molybdate are further reduced again, prepare very difficulty of highly purified ammonium tetramolybdate.The purification purification process of existing ammonium molybdate is to carry out in the aqueous solution mostly, and the method for purification is a lot, for example recrystallization, chemical precipitation, evaporative crystallization, ion-exchange and organic solvent extraction etc.These methods have many saving graces, but exist many weak points on purification process and the purification effect, therefore, also do not have a kind of ammonium molybdate purifying and impurity-removing method that can obtain the ammonium tetramolybdate of purity 〉=99.998% at present.
Summary of the invention
At the defective of now still not having the ammonium tetramolybdate of purity 〉=99.998%, the preparation method who the purpose of this invention is to provide a kind of high purity ammonium tetramolybdate, specifically, the further impurity-removing method that relates to a kind of ammonium tetramolybdate, described preparation method is simple, purification effect good, ammonium tetramolybdate purity 〉=99.998% for preparing, Fisher particle size≤0.3 μ m.
The present invention is achieved by the following technical solutions.
A kind of preparation method of high purity ammonium tetramolybdate, its preparation method concrete steps are as follows:
(1) pure water is mixed with concentrated nitric acid, stir under the room temperature, obtain mixing solutions 1, mixing solutions 1 is heated to 〉=80 ℃, add the raw material ammonium tetramolybdate till the mixing solutions 1 beginning muddiness with the speed of 1～5g/min, 90～95 ℃ of stirring reaction 1～3h, the naturally cooling ageing is to room temperature, filter, the solid after filtering is got filter cake 1 with the pure water washing more than 2 times.
Wherein, described raw material ammonium tetramolybdate is a national standard secondary ammonium tetramolybdate, the H of mixing solutions 1
+Concentration 〉=3mol/L, preferred feedstock ammonium tetramolybdate (Kg): mixing solutions 1 (L)=1.0: 3.0～6.0.
(2) filter cake 1 is mixed with pure water, obtain solidliquid mixture 1, will be heated to 90～95 ℃ under solidliquid mixture 1 whipped state, keep 0.5～2h, filter, the solid after filtering is obtained filter cake 2 with the pure water washing more than 2 times.
Wherein, described filter cake 1 (Kg): pure water (L)=1.0: 3.0～5.0.
(3) filter cake 2 is mixed with pure water, obtains solidliquid mixture 2, be heated under solidliquid mixture 2 whipped states 〉=80 ℃, adding dilute hydrochloric acid to pH value is 0.5～1, reaction 30～60min down in temperature 〉=80 ℃ filters, and the solid after filtering is obtained filter cake 3 with the pure water washing more than 2 times.
Wherein, described filter cake 2 (Kg): pure water (L)=1.0: 3.0～5.0, hydrochloric acid and water volume ratio are 1.0: 3.0～4.0 in the dilute hydrochloric acid.
(4) filter cake 3 is mixed with pure water and strong aqua, stirring and dissolving under the room temperature is filtered then, obtains filtrate 1, under the agitation condition, with pure water and concentrated nitric acid the density of filtrate 1 is transferred to 1.20～1.26g/cm
3, the pH value is 6.0～7.0, obtains mixing solutions 2, and adding concentrated nitric acid to pH value in mixing solutions 2 is 2.5～4.0, filters, and the solid that filtration is obtained more than 2 times, obtains filter cake 4 with the pure water washing.
Wherein, described filter cake 3 (Kg): pure water (L): strong aqua (L)=1.0: 1.0～1.1: 0.5.
(5) filter cake 4 is mixed with pure water and strong aqua, stirring and dissolving obtains mixing solutions 3, and at 0.04～0.09MPa, reduction vaporization crystallizes to and crystallisate occurs under 60～80 ℃ of conditions, is cooled to room temperature with mixing solutions 3, filters, and obtains filter cake 5.
Wherein, described filter cake 4 (Kg): pure water (L): strong aqua (L)=1.0: 1.0～1.1: 0.5, preferred reduction vaporization crystallizes to 1/3 moisture content that evaporates mixing solutions 3 cumulative volumes.
(6) filter cake 5 is mixed with pure water and strong aqua, stirring and dissolving obtains mixing solutions 4, with pure water, concentrated nitric acid or strong aqua the density of mixing solutions 4 is transferred to 1.18～1.20g/cm
3, pH value is 7.0～9.0, being heated to temperature is 50～55 ℃, adding concentrated nitric acid to the pH value of mixing solutions 4 is 2.0～3.0, filters, and the solid that filtration is obtained is with the pure water washing more than 2 times, obtain filter cake 6, ℃ oven dry down in temperature≤120, the moisture content in filter cake 6 is reduced to≤1.0g/cm
3, prepare a kind of purity 〉=99.998%, the ammonium tetramolybdate of Fisher particle size≤0.3 μ m.
Wherein, filter cake 5 (Kg): pure water (L): strong aqua (L)=1.0: 1.0～1.1: 0.5.
Wherein, the pure water that relates among the present invention is the water of purity 〉=industrial pure water purity, and the purity 〉=top grade of unexplained reference agents useful for same strong aqua, concentrated nitric acid and concentrated hydrochloric acid is pure.
Adopt the purity of the ammonium tetramolybdate that the preparation method of a kind of high purity ammonium tetramolybdate provided by the invention prepares to adopt the ICP-MS method to carry out analytical test, record purity 〉=99.998% of ammonium tetramolybdate.
Beneficial effect
1. the preparation method of a kind of high purity ammonium tetramolybdate provided by the invention, equipment used is simple and few, and equipment failure is got rid of easily, but the utilization of equipment recirculation reduces facility investment;
2. the preparation method of a kind of high purity ammonium tetramolybdate provided by the invention carries out under the sealing decompression, and molybdenum total losses amount is little, and the rate of recovery reduces waste gas and discharging of waste liquid more than 98%;
3. the preparation method of a kind of high purity ammonium tetramolybdate provided by the invention, technology and simple to operate, labour intensity is little, the level of automation height, parameter is controlled easily;
4. the preparation method of a kind of high purity ammonium tetramolybdate provided by the invention, all filtrates, debris and filter residue all reclaim the preparation ammonium tetramolybdate, and the recirculation utilization reduces raw materials cost, reduces waste liquid and waste sludge discharge; Reagent obtains efficient recovery during evaporative crystallization, improves the utilization ratio of reagent, reduces reagent cost, reduces environmental pollution;
5. the preparation method of a kind of high purity ammonium tetramolybdate provided by the invention can effectively reduce foreign matter content in the ammonium molybdate, particularly potassium and tungsten, effect is very obvious, impurity U, Th content can drop to the ppb level, and ammonium tetramolybdate purity is increased substantially, and satisfy the requirement of electronic industry.And the constant product quality of preparation, purity 〉=99.998%, Fisher particle size≤0.3 μ m.Especially on the preparation high pure molybdenum powder, have bigger development potentiality.
Embodiment
In order to prove absolutely characteristic of the present invention and to implement mode of the present invention, provide embodiment below.
The ammonium tetramolybdate of raw material described in following examples is national standard secondary (MSA-2) ammonium tetramolybdate, and the pure water that relates to is industrial pure water, and the unexplained reference agents useful for same is commercially available, and its purity is that top grade is pure; The purity of the ammonium tetramolybdate for preparing among the embodiment all adopts the ICP-MS method to carry out analytical test.
Embodiment 1
Measure pure water 1200mL, concentrated nitric acid 600mL puts into the poly-tetrafluoro container with whipping appts, mixes under the room temperature, obtain mixing solutions 1, mixing solutions 1 is heated to 80 ℃, adds the raw material ammonium tetramolybdate till the mixing solutions 1 beginning muddiness with the speed of 5g/min, the add-on of raw material ammonium tetramolybdate is 300g, 90 ℃ of stirring reaction 1h, the naturally cooling ageing is filtered to room temperature, and the solid after filtering is got filter cake 12 times with the pure water washing.
Filter cake 1 is mixed filter cake 1 (Kg) with pure water: pure water (L)=1.0: 3.0, obtain solidliquid mixture 1, will be heated to 95 ℃ under solidliquid mixture 1 whipped state, keep 1h, filter at once, the solid after filtering is obtained filter cake 22 times with the pure water washing.
Filter cake 2 is mixed with pure water, filter cake 2 (Kg): pure water (L)=1.0: 3.0, obtain solidliquid mixture 2, to be heated to 85 ℃ under solidliquid mixture 2 whipped states, add dilute hydrochloric acid, hydrochloric acid volume in the described dilute hydrochloric acid: volume of water=1.0: 3.0, adjust pH is 0.5,85 ℃ of reaction 30min filter at once, and the solid after filtering is obtained filter cake 32 times with the pure water washing.
Filter cake 3 is mixed filter cake 3 (Kg) with pure water and strong aqua: pure water (L): strong aqua (L)=1.0: 1.0: 0.5, stirring and dissolving under the room temperature is filtered then, obtains filtrate 1, under the agitation condition, with pure water and concentrated nitric acid the density of filtrate 1 is transferred to 1.26g/cm
3, the pH value is 7.0, obtains mixing solutions 2, and adding concentrated nitric acid to pH value in mixing solutions 2 is 2.5, filters, and the solid that filtration is obtained washs 2 times with pure water, obtains filter cake 4.
Filter cake 4 is mixed with pure water and strong aqua, filter cake 4 (Kg): pure water (L): strong aqua (L)=1.0: 1.0: 0.5, stirring and dissolving under the room temperature, obtain mixing solutions 3, mixing solutions 3 at 0.04MPa, is obtained crystallisate after reduction vaporization crystallizes to 1/3 moisture content that evaporates mixing solutions 3 cumulative volumes under 80 ℃ of conditions, be cooled to room temperature, filter, obtain filter cake 5.
Filter cake 5 is mixed filter cake 5 (Kg) with pure water and strong aqua: pure water (L): strong aqua (L)=1.0: 1.0: 0.5, stirring and dissolving under the room temperature obtains mixing solutions 4, with pure water and concentrated nitric acid the density of mixing solutions 4 is transferred to 1.20g/cm
3, the pH value is 7.0, and being heated to temperature is 50 ℃, and adding concentrated nitric acid to the pH value of mixing solutions 4 is 2.0, filters at once, and the solid that filtration is obtained washs 2 times with pure water, obtains filter cake 6, toasts 2h down for 120 ℃ in temperature, and the moisture content in filter cake 6 is reduced to 1.0g/cm
3, preparing purity is that Fisher particle size is the high purity ammonium tetramolybdate crystal of 0.30 μ m greater than 99.9983%.
Impurity U and Th content are all less than 0.1ppb in the high purity ammonium tetramolybdate crystal that present embodiment prepares.
Other foreign matter content in the ammonium tetramolybdate crystal that present embodiment prepares is as shown in table 1.
The ammonium tetramolybdate foreign matter content (ppm) that table 1 embodiment 1 prepares
Embodiment 2
Measure pure water 1200mL, concentrated nitric acid 650mL puts into the poly-tetrafluoro container with whipping appts, mixes under the room temperature, obtain mixing solutions 1, mixing solutions 1 is heated to 90 ℃, adds till the raw material ammonium tetramolybdate begins muddiness to mixing solutions with the speed of 2g/min, the add-on of raw material ammonium tetramolybdate is 320g, 95 ℃ of stirring reaction 2h, the naturally cooling ageing is filtered to room temperature, and the solid after filtering is got filter cake 13 times with the pure water washing.
Filter cake 1 is mixed filter cake 1 (Kg) with pure water: pure water (L)=1.0: 4.0, obtain solidliquid mixture 1, will be heated to 95 ℃ under solidliquid mixture 1 whipped state, keep 1.5h, filter at once, the solid after filtering is obtained filter cake 23 times with the pure water washing.
Filter cake 2 is mixed with pure water, filter cake 2 (Kg): pure water (L)=1.0: 4.0, obtain solidliquid mixture 2, to be heated to 95 ℃ under solidliquid mixture 2 whipped states, add dilute hydrochloric acid, hydrochloric acid volume in the described dilute hydrochloric acid: volume of water=1.0: 3.5, adjust pH is 0.8,95 ℃ of reaction 40min filter at once, and the solid after filtering is obtained filter cake 33 times with the pure water washing.
Filter cake 3 is mixed filter cake 3 (Kg) with pure water and strong aqua: pure water (L): strong aqua (L)=1.0: 1.05: 0.5, stirring and dissolving under the room temperature is filtered then, obtains filtrate 1, under the agitation condition, with pure water and concentrated nitric acid the density of filtrate 1 is transferred to 1.24g/cm
3, the pH value is 6.5, obtains mixing solutions 2, and adding concentrated nitric acid to pH value in mixing solutions 2 is 3.0, filters, and the solid that filtration is obtained washs 3 times with pure water, obtains filter cake 4.
Filter cake 4 is mixed with pure water and strong aqua, filter cake 4 (Kg): pure water (L): strong aqua (L)=1.0: 1.05: 0.5, stirring and dissolving under the room temperature, obtain mixing solutions 3, mixing solutions 3 at 0.06MPa, is obtained crystallisate after reduction vaporization crystallizes to 1/3 moisture content that evaporates mixing solutions 3 cumulative volumes under 70 ℃ of conditions, be cooled to room temperature, filter, obtain filter cake 5.
Filter cake 5 is mixed filter cake 5 (Kg) with pure water and strong aqua: pure water (L): strong aqua (L)=1.0: 1.05: 0.5, stirring and dissolving under the room temperature obtains mixing solutions 4, with pure water and strong aqua the density of mixing solutions 4 is transferred to 1.19g/cm
3, the pH value is 9.0, being heated to temperature is 52 ℃, adding concentrated nitric acid to the pH value of mixing solutions 4 is 2.5, filters at once, and the solid that filtration is obtained washs 3 times with pure water, obtain filter cake 6, toast 2.5h down for 110 ℃ in temperature, the moisture content in filter cake 6 is reduced to 0.9g/cm
3, preparing purity is that Fisher particle size is the high purity ammonium tetramolybdate crystal of 0.25 μ m greater than 99.9983%.
Impurity U and Th content are all less than 0.1ppb in the high purity ammonium tetramolybdate that present embodiment prepares.
Other foreign matter content in the ammonium tetramolybdate crystal that present embodiment prepares is as shown in table 2.
The ammonium tetramolybdate foreign matter content (ppm) that table 2 embodiment 2 prepares
Embodiment 3
Measure pure water 1200mL, concentrated nitric acid 700mL puts into the poly-tetrafluoro container with whipping appts, mixes under the room temperature, obtain mixing solutions 1, mixing solutions 1 is heated to 92 ℃, adds till the raw material ammonium tetramolybdate begins muddiness to mixing solutions with the speed of 1g/min, the add-on of raw material ammonium tetramolybdate is 350g, 95 ℃ of stirring reaction 3h, the naturally cooling ageing is filtered to room temperature, and the solid after filtering is got filter cake 14 times with the pure water washing;
Filter cake 1 is mixed filter cake 1 (Kg) with pure water: pure water (L)=1.0: 5.0, obtain solidliquid mixture 1, will be heated to 95 ℃ under solidliquid mixture 1 whipped state, keep 2h, filter at once, the solid after filtering is obtained filter cake 24 times with the pure water washing.
Filter cake 2 is mixed with pure water, filter cake 2 (Kg): pure water (L)=1.0: 5.0, obtain solidliquid mixture 2, to be heated to 95 ℃ under solidliquid mixture 2 whipped states, add dilute hydrochloric acid, hydrochloric acid volume in the described dilute hydrochloric acid: volume of water=1.0: 4.0, adjust pH is 1,95 ℃ of reaction 60min filter at once, and the solid after filtering is obtained filter cake 34 times with the pure water washing.
Filter cake 3 is mixed filter cake 3 (Kg) with pure water and strong aqua: pure water (L): strong aqua (L)=1.0: 1.1: 0.5, stirring and dissolving under the room temperature is filtered then, obtains filtrate 1, under the agitation condition, with pure water and concentrated nitric acid the density of filtrate 1 is transferred to 1.20g/cm
3, the pH value is 6.0, obtains mixing solutions 2, and adding concentrated nitric acid to pH value in mixing solutions 2 is 4.0, filters, and the solid that filtration is obtained washs 4 times with pure water, obtains filter cake 4.
Filter cake 4 is mixed with pure water and strong aqua, filter cake 4 (Kg): pure water (L): strong aqua (L)=1.0: 1.1: 0.5, stirring and dissolving under the room temperature, obtain mixing solutions 3, mixing solutions 3 at 0.09MPa, is obtained crystallisate after reduction vaporization crystallizes to 1/3 moisture content that evaporates mixing solutions 3 cumulative volumes under 60 ℃ of conditions, be cooled to room temperature, filter, obtain filter cake 5.
Filter cake 5 is mixed filter cake 5 (Kg) with pure water and strong aqua: pure water (L): strong aqua (L)=1.0: 1.1: 0.5, stirring and dissolving under the room temperature obtains mixing solutions 4, with pure water and strong aqua the density of mixing solutions 4 is transferred to 1.18g/cm
3, the pH value is 8.0, and being heated to temperature is 55 ℃, and adding concentrated nitric acid to the pH value of mixing solutions 4 is 3.0, filters at once, and the solid that filtration is obtained washs 4 times with pure water, obtains filter cake 6, toasts 3h down for 100 ℃ in temperature, and the moisture content in filter cake 6 is reduced to 0.80g/cm
3, preparing purity is that Fisher particle size is the high purity ammonium tetramolybdate crystal of 0.20 μ m greater than 99.9983%.
Impurity U and Th content are all less than 0.1ppb in the high purity ammonium tetramolybdate that present embodiment prepares.
Other foreign matter content in the ammonium tetramolybdate crystal that present embodiment prepares is as shown in table 3.
The ammonium tetramolybdate foreign matter content (ppm) that table 3 embodiment 3 prepares
The present invention includes but be not limited to above embodiment, every any being equal to of carrying out under the spirit and principles in the present invention, replace or local improvement, all will be considered as within protection scope of the present invention.
Claims (3)
1. the preparation method of a high purity ammonium tetramolybdate, it is characterized in that: described preparation method's concrete steps are as follows:
(1) pure water is mixed with concentrated nitric acid, stir under the room temperature, obtain mixing solutions 1, mixing solutions 1 is heated to 〉=80 ℃, add the raw material ammonium tetramolybdate till the mixing solutions 1 beginning muddiness with the speed of 1～5g/min, 90～95 ℃ of stirring reaction 1～3h, the naturally cooling ageing is to room temperature, filter, the solid after filtering is got filter cake 1 with the pure water washing more than 2 times;
(2) filter cake 1 is mixed with pure water, obtain solidliquid mixture 1, will be heated to 90～95 ℃ under solidliquid mixture 1 whipped state, keep 0.5～2h, filter, the solid after filtering is obtained filter cake 2 with the pure water washing more than 2 times;
(3) filter cake 2 is mixed with pure water, obtains solidliquid mixture 2, be heated under solidliquid mixture 2 whipped states 〉=80 ℃, adding dilute hydrochloric acid to pH value is 0.5～1, reaction 30～60min down in temperature 〉=80 ℃ filters, and the solid after filtering is obtained filter cake 3 with the pure water washing more than 2 times;
(4) filter cake 3 is mixed with pure water and strong aqua, stirring and dissolving under the room temperature is filtered then, obtains filtrate 1, under the agitation condition, with pure water and concentrated nitric acid the density of filtrate 1 is transferred to 1.20～1.26g/cm
3, the pH value is 6.0～7.0, obtains mixing solutions 2, and adding concentrated nitric acid to pH value in mixing solutions 2 is 2.5～4.0, filters, and the solid that filtration is obtained more than 2 times, obtains filter cake 4 with the pure water washing;
(5) filter cake 4 is mixed with pure water and strong aqua, stirring and dissolving obtains mixing solutions 3, and at 0.04～0.09MPa, reduction vaporization crystallizes to and crystallisate occurs under 60～80 ℃ of conditions with mixing solutions 3, when being cooled to room temperature, filters, and obtains filter cake 5;
(6) filter cake 5 is mixed with pure water and strong aqua, stirring and dissolving obtains mixing solutions 4, with pure water, concentrated nitric acid or strong aqua the density of mixing solutions 4 is transferred to 1.18～1.20g/cm
3, the pH value is 7.0～9.0, being heated to temperature is 50～55 ℃, adding concentrated nitric acid to the pH value of mixing solutions 4 is 2.0～3.0, filters, and the solid that filtration is obtained washs more than 2 times with pure water, obtain filter cake 6, ℃ oven dry down in temperature≤120, the moisture content in filter cake 6 is reduced to≤1.0g/cm
3, prepare the ammonium tetramolybdate of a kind of purity 〉=99.998%;
Wherein, the described raw material ammonium tetramolybdate of step (1) is a national standard secondary ammonium tetramolybdate, the H of mixing solutions 1
+Concentration 〉=3mol/L;
The described filter cake 1 of step (2) (Kg): pure water (L)=1.0: 3.0～5.0;
The described filter cake 2 of step (3) (Kg): pure water (L)=1.0: 3.0～5.0, hydrochloric acid and water volume ratio are 1.0: 3.0～4.0 in the dilute hydrochloric acid;
The described filter cake 3 of step (4) (Kg): pure water (L): strong aqua (L)=1.0: 1.0～1.1: 0.5;
The described filter cake 4 of step (5) (Kg): pure water (L): strong aqua (L)=1.0: 1.0～1.1: 0.5;
The described filter cake 5 of step (6) (Kg): pure water (L): strong aqua (L)=1.0: 1.0～1.1: 0.5;
Described pure water is the water of purity 〉=industrial pure water purity, and the purity 〉=top grade of agents useful for same strong aqua, concentrated nitric acid, concentrated hydrochloric acid is pure.
2. the preparation method of a kind of high purity ammonium tetramolybdate according to claim 1 is characterized in that: raw material ammonium tetramolybdate (Kg) in the step (1): mixing solutions 1 (L)=1.0: 3.0～6.0.
3. the preparation method of a kind of high purity ammonium tetramolybdate according to claim 1 is characterized in that: reduction vaporization crystallizes to 1/3 moisture content that evaporates mixing solutions 3 cumulative volumes in the step (5).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103265079A (en) * | 2013-06-05 | 2013-08-28 | 杭州临安慧尔钼业科技有限公司 | Method for recovering molybdenum from molybdenum containing waste acid of filament wire |
| CN103663561A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Recycling method of molybdenum in filament-melting waste acid |
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| US4555386A (en) * | 1984-02-29 | 1985-11-26 | Gte Products Corporation | Process for purifying molybdenum trioxide |
| CN101492181A (en) * | 2009-02-20 | 2009-07-29 | 中南大学 | Method for removing tungsten, vanadium, phosphor and arsenic from molybdate solution by deposition |
| CN101913653A (en) * | 2010-09-02 | 2010-12-15 | 江西铜业股份有限公司 | Method for controlling structure of ammonium molybdate crystal |
| CN101987747A (en) * | 2009-08-05 | 2011-03-23 | 天津市化学试剂研究所 | Preparation method of reagent-grade ammonium molybdate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4555386A (en) * | 1984-02-29 | 1985-11-26 | Gte Products Corporation | Process for purifying molybdenum trioxide |
| CN101492181A (en) * | 2009-02-20 | 2009-07-29 | 中南大学 | Method for removing tungsten, vanadium, phosphor and arsenic from molybdate solution by deposition |
| CN101987747A (en) * | 2009-08-05 | 2011-03-23 | 天津市化学试剂研究所 | Preparation method of reagent-grade ammonium molybdate |
| CN101913653A (en) * | 2010-09-02 | 2010-12-15 | 江西铜业股份有限公司 | Method for controlling structure of ammonium molybdate crystal |
Cited By (3)
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| CN103663561A (en) * | 2012-09-10 | 2014-03-26 | 中国石油化工股份有限公司 | Recycling method of molybdenum in filament-melting waste acid |
| CN103265079A (en) * | 2013-06-05 | 2013-08-28 | 杭州临安慧尔钼业科技有限公司 | Method for recovering molybdenum from molybdenum containing waste acid of filament wire |
| CN103265079B (en) * | 2013-06-05 | 2015-08-12 | 杭州临安慧尔钼业科技有限公司 | A kind of from filament wire containing the method reclaiming molybdenum molybdenum spent acid |
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