CN107860639A - A kind of titanium dioxide resolution of no hydrofluoric acid and separation method - Google Patents
A kind of titanium dioxide resolution of no hydrofluoric acid and separation method Download PDFInfo
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- CN107860639A CN107860639A CN201710924209.0A CN201710924209A CN107860639A CN 107860639 A CN107860639 A CN 107860639A CN 201710924209 A CN201710924209 A CN 201710924209A CN 107860639 A CN107860639 A CN 107860639A
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- oxalic acid
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 24
- 238000000926 separation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000005349 anion exchange Methods 0.000 claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims abstract description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 85
- 239000000243 solution Substances 0.000 claims description 55
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 235000006408 oxalic acid Nutrition 0.000 claims description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 239000004332 silver Substances 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 7
- 239000011347 resin Substances 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 241000370738 Chlorion Species 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 abstract description 6
- 238000004458 analytical method Methods 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 abstract description 3
- 238000002955 isolation Methods 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000000100 multiple collector inductively coupled plasma mass spectrometry Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 238000011084 recovery Methods 0.000 description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 210000001519 tissue Anatomy 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000000120 microwave digestion Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 108010033040 Histones Proteins 0.000 description 1
- 206010021027 Hypomagnesaemia Diseases 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 208000006735 Periostitis Diseases 0.000 description 1
- 208000025865 Ulcer Diseases 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 210000000748 cardiovascular system Anatomy 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 210000003460 periosteum Anatomy 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 108010048734 sclerotin Proteins 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 238000004454 trace mineral analysis Methods 0.000 description 1
- 231100000397 ulcer Toxicity 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to sample pre-treatments field, there is provided a kind of titanium dioxide resolution of no hydrofluoric acid and separation method.The present invention is cleared up using alkali fusion to titanium dioxide, and the isolation of purified of titanium elements in sample is realized using anion-exchange column, so as to reach such as ICP MS, ICP OES, MP AES, MC ICP MS instruments analysis requirement.This method avoid the use of hydrofluoric acid in conventional method, there is convenient and swift environmental protection, titanium ion separating degree is high, the advantages that free from admixture ion interference.
Description
Technical field
The present invention relates to sample pre-treatments field, and in particular to a kind of titanium dioxide resolution of no hydrofluoric acid and separation method
Background technology
Titanium is the metallic element containing flow control ten in the earth's crust, and with current scientific and technological development, titanium is widely applied by people
In chemical industry, oil, electric power, desalinization, building and daily life.Titanium dioxide is the most important compound of titanium elements.Two
Titanium oxide has a wide range of applications in human being's production and life.In such applications, titanium dioxide would generally be with nano particle
Form used.
Compared with normal size particle, its property has larger difference to the particle of nano-scale.Nano titanium oxide has good
Optical property, possess the property not available for conventional material because its grain diameter is small, specific surface area is big, as light is urged
The function such as change effect and ultraviolet screener, in fields such as auto industry, sun care preparations, wastewater treatment, sterilization, ceramics, coating
There is extensive purposes.In recent years, environmental exposure and security of the titania nanoparticles to human body and other biological body
Gradually cause the attention of scientific research personnel.For the titanium dioxide in research environment and Biomedia, it is necessary to can be to medium
In titanium dioxide carry out accurate Qualitative and quantitative analysis, this has required reliable and effective method to come to different types of sample
Product are cleared up and isolation of purified.
Hydrofluoric acid and nitric acid are used in the method for traditional resolution titanium dioxide.Hydrofluoric acid to clothing, skin, eyes,
Respiratory tract, gastrointestinal mucosal have stimulation, corrosiveness.Fluorine ion, which enters blood or tissue, to be combined with its calcium ions and magnesium ions, make
It turns into insoluble or sl. sol. calcirm-fluoride and magnesium fluoride, and is possible to directly block blood vessel, directly or indirectly influences nervous centralis
The function of system and cardiovascular system, cause low blood calcium, hypomagnesemia syndrome.In addition, hydrofluoric acid can cause contact site substantially to burn
Wound, histone is dehydrated and is dissolved, cuticula can be readily penetrated through, penetrate into deep tissue, dissolve cell membrane, cause tissue fluid
Change, severe one can make bone turn into calcirm-fluoride, form the ulcer of indolence as deep as periosteum and sclerotin.
Document report at present on resolution and the analysis of the sample containing titanium elements is also fewer.《Environmental Chemistry》2013 4
Month the 4th phase of volume 32 Liu Zhiyuans of page 666, in water conservancy et al. " influence of the different digestion procedures to nano titanium oxide concentration mensuration "
Paper give current three classes resolution titanium dioxide method i.e. Microwave Digestion, heating plate resolution method and ammonium persulfate alkali fusion
The rate of recovery of method.Hydrofluoric acid nitric acid Microwave Digestion is drawn after being determined by inductively coupled plasma spectrometer (ICP-OES)
The rate of recovery can reach 109%, but hydrofluoric acid resolution method is larger to human body and environmental hazard, and ammonium persulfate alkali fusion
The rate of recovery is than relatively low, only 63% or so.When the application above method carries out trace analysis, the micro interference element in part can not
Thoroughly remove, it is impossible to reach experimental analysis requirement, the Instrumental Analysis such as ICP-MS, ICP-OES of complex matrices sample can not be carried out.
It is being published in《Analytical chemistry research report》Another piece of the 12nd phase page 1830~1835 of volume 39 in December, 2011
In document report, Tang Suohan, Zhu Xiangkun et al. are in " ionic energy transfer and more reception ICP-MS high-precision measuring titaniums
The text of the composition of isotope " one also reports is used for specimen preprocessing using ionic energy transfer method and hydrofluoric acid as eluant, eluent
Reason.
In the present invention, cleared up using potassium hydroxide alkali fusion method, and make use of oxalic acid and titanium ion stable complexation
Property, using oxalic acid substitute hydrofluoric acid as eluant, eluent, method whole process without using hydrofluoric acid, test indicate that, this method is net
Change efficiency high, the titanium ion rate of recovery in simple and safe operation and sample solution is high, the titaniferous sample available for different purposes
Resolution, separation and purification.
The content of the invention
The embodiment of the present invention provides a kind of sample-pretreating method cleared up and separated to titanium dioxide, need not using knowing clearly
Hydrofluoric acid can carry out the sample-pretreating method of titanium dioxide resolution, and experimentation is very safe, and can remove well dry
Ion is disturbed, purifies matrix.
The embodiment of the present invention provides a kind of sample-pretreating method cleared up and separated to titanium dioxide, including following step
Suddenly：
1) the resolution processing of sample
By titanium dioxide and KOH solids according to 1:10 mass ratio mixing is placed in silver crucible, is positioned under Muffle furnace
600-700 DEG C of reaction 50-70min, after being cooled to room temperature, appropriate 1mol/L watery hydrochloric acid, ultrasonic 2h are added into silver crucible
Or stand overnight, obtained the first solution to be measured of clarification is put into stand-by in centrifuge tube；
2) the foreign ion separation of the first solution to be measured
The described first appropriate solution to be measured is taken to be mixed with 0.5mol/L oxalic acid solutions, wherein first taken solution to be measured
In quality and the oxalic acid mass ratio of titanium elements be 1:375, mixed solution is added to pretreated anion exchange
On post, and ion elution is carried out respectively according to following order：0.5mol/L oxalic acid solution, 0.48mol/L oxalic acid and
0.36mol/L hydrochloric acid mixed solution, 9mol/L hydrochloric acid solution, the solution of final step is collected as the second solution to be measured；
3) chlorion of the second solution to be measured is removed
Take appropriate above-mentioned second solution to be measured to be put into polytetrafluoroethylene (PTFE) crucible, appropriate concentrated nitric acid is added, in 160~180
DEG C it is evaporated, closeing the lid and be put into Muffle furnace 180 DEG C or so and be heated to solid crucible disappears, and is added in most backward crucible
5% salpeter solution dilutes, you can obtains the simple titanium ion of matrix solution to be measured.
Further, the titanium dioxide is nano titanium oxide.
Further, in step 2), the dosage point of the oxalic acid solution of ion elution, oxalic acid and hydrochloric acid mixed solution is carried out
Wei not 5mL, 10mL.
Further, in step 2), the amount of the described first solution to be measured taken is 0.2mL, and the amount of oxalic acid solution is
5mL。
Further, in step 2), the amount of the described first solution to be measured taken is 0.1mL, and the amount of oxalic acid solution is
5mL。
Further, in step 2), in addition to the step of cleaned to anion-exchange column, the cleaning step includes：
Weigh AG1-X8 resin anion (R.A.)s 12-15g, ultra-pure water 16-20g is placed in beaker and mixes and place 12h, by the moon from
Sub- resin mixture liquor, which is fitted into after anion-exchange column, sequentially adds ultra-pure water, HNO into anion-exchange column3, HCl, oxalic acid it is molten
Liquid is cleaned.
The experimental principle that the present invention can be reacted using titanium dioxide with alkali, devising can be carried out without hydrofluoric acid
The sample-pretreating method of titanium dioxide resolution, avoids laboratory technician and touches the danger that hydrofluoric acid is brought, and method is simpler,
Safe operation process.Also, the separation of anion-exchange column is carried out using the complexing of oxalate denominationby and titanium ion, it is right
In complex matrices sample, it can be very good to remove interfering ion, purify matrix.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also basis
These accompanying drawings obtain other accompanying drawings.
Fig. 1 nano titanium oxides alkali fusion clears up rate of recovery figure；
Fig. 2 clears up liquid through ion exchange post separation situation.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below by the technology in the embodiment of the present invention
Scheme is clearly and completely described, it is clear that and described embodiment is part of the embodiment of the present invention, rather than whole
Embodiment.Based on the embodiment in the present invention, those of ordinary skill in the art are obtained under the premise of creative work is not paid
The every other embodiment obtained, belongs to the scope of protection of the invention.
The embodiment of the present invention 1 provides a kind of sample-pretreating method cleared up and separated to titanium dioxide, including following step
Suddenly：
1) the resolution processing of sample
10mg titanium dioxide, e.g. nano titanium oxide are taken, it is mixed with 100mg KOH solids and is placed in silver crucible
It is interior, the lower 650 DEG C of reactions 1h of Muffle furnace is positioned over, after being down to room temperature, 1mol/L watery hydrochloric acid 10mL, ultrasound are added into silver crucible
Treat that solid all dissolves, obtained the first solution to be measured of clarification is put into stand-by in 15mL centrifuge tubes.
2) the foreign ion separation of the first testing liquid
Weigh AG1-X8 resin anion (R.A.)s 12g, ultra-pure water 16g is placed in beaker and mixes and place 12h, by resin anion (R.A.)
Mixed liquor, which is fitted into after anion-exchange column into anion-exchange column, sequentially adds 5mL ultra-pure waters, 3mL 7mol/L HNO3、3mL
9mol/L HCl, 15mL 0.5mol/L oxalic acid solution are cleaned, and then take above-mentioned first testing liquid 0.2mL and 5mL
0.5mol/L oxalic acid solution mixing, is added on cleaned anion-exchange column, and carried out respectively according to following order
Ion elution, the mixed in hydrochloric acid of 5mL 0.5mol/L oxalic acid solution, 10mL 0.48mol/L oxalic acid and 0.36mol/L are molten
The hydrochloric acid solution of liquid, 20mL 9mol/L, last 20mL is collected as the second prepare liquid.
3) chlorion of the second testing liquid is removed
Take above-mentioned 20mL the second testing liquid to be put into polytetrafluoroethylene (PTFE) crucible, add 5mL concentrated nitric acids, in 170 DEG C of steamings
Dry, closeing the lid and be put into Muffle furnace 180 DEG C and be heated to solid crucible disappears (about 20min).Add in most backward crucible
Enter 5% salpeter solution and be diluted to 10mL, you can obtain the simple titanium ion of matrix solution to be measured.
The embodiment of the present invention 2 provides a kind of sample-pretreating method cleared up and separated to titanium dioxide, including following step
Suddenly：
1) the resolution processing of sample
20mg nano titanium oxide samples, e.g. nano titanium oxide are taken, and it is mixed with 200mgKOH solids and put
In in silver crucible, being positioned over the lower 700 DEG C of reactions 1h of Muffle furnace, after being down to room temperature, 1mol/L watery hydrochloric acid is added into silver crucible
10mL, stand overnight, obtained the first solution to be measured of clarification is put into stand-by in 50mL centrifuge tubes.
2) the foreign ion separation of the first testing liquid
Weigh AG1-X8 resin anion (R.A.)s 15g, ultra-pure water 20g is placed in beaker and mixes and place 12h, by resin anion (R.A.)
Mixed liquor, which is fitted into after anion-exchange column into anion-exchange column, sequentially adds 10mL ultra-pure waters, 5mL 7mol/L HNO3、
5mL 9mol/L HCl, 20mL 0.5mol/L oxalic acid solution are cleaned, then take above-mentioned first testing liquid 0.1mL with
5mL 0.5mol/L oxalic acid solution mixing, is added on cleaned anion-exchange column, and distinguish according to following order
Carry out ion elution, 5mL 0.5mol/L oxalic acid solution, 10mL 0.48mol/L oxalic acid and 0.36mol/L mixed in hydrochloric acid
The hydrochloric acid solution of solution, 20mL 9mol/L, last 20mL is collected as the second prepare liquid.
3) chlorion of the second testing liquid is removed
Take above-mentioned second testing liquid 20mL to be put into polytetrafluoroethylene (PTFE) crucible, add 5mL concentrated nitric acids, be evaporated in 180 DEG C,
Crucible is closed the lid and is put into Muffle furnace 185 DEG C and is heated to solid and disappears (about 20min).Added in most backward crucible
5% salpeter solution is diluted to 10mL, you can obtains the simple titanium ion of matrix solution to be measured.
The measure of titanium ion concentration is carried out by above-mentioned steps, it is as shown in the table to be recycled rate：
| Sample number into spectrum | Sample ID | Recovery of standard addition/% |
| 1 | 15nm nano titanium oxides (anatase titanium dioxide) | 103.56 |
| 2 | 32nm nano titanium oxides (anatase titanium dioxide) | 102.79 |
| 3 | 25nm nano titanium oxides (rutile-type) | 100.57 |
| 4 | 40nm nano titanium oxides (anatase titanium dioxide) | 96.88 |
| 5 | P25 nano titanium oxides (anatase titanium dioxide) | 98.84 |
| 6 | 60nm nano titanium oxides (rutile-type) | 97.46 |
| 7 | 100nm nano titanium oxides (rutile-type) | 93.65 |
| 8 | 100nm nano titanium oxides (anatase titanium dioxide) | 95.58 |
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, it will be understood by those within the art that：It still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic；
And these modification or replace, do not make appropriate technical solution essence depart from various embodiments of the present invention technical scheme spirit and
Scope.
Claims (6)
1. a kind of titanium dioxide resolution of no hydrofluoric acid and separation method, it is characterised in that comprise the following steps：
1) the resolution processing of sample
By titanium dioxide and KOH solids according to 1:10 mass ratio mixing is placed in silver crucible, be positioned over 600 under Muffle furnace~
700 DEG C of 50~70min of reaction, after being cooled to room temperature, add appropriate 1mol/L watery hydrochloric acid into silver crucible, ultrasonic 2h or put
Put overnight, obtained the first solution to be measured of clarification is put into stand-by in centrifuge tube；
2) the foreign ion separation of the first solution to be measured
The described first appropriate solution to be measured is taken to be mixed with 0.5mol/L oxalic acid solutions, wherein in first taken solution to be measured
The quality of titanium elements is 1 with oxalic acid mass ratio:375, mixed solution is added on pretreated anion-exchange column,
And ion elution is carried out respectively according to following order：0.5mol/L oxalic acid solution, 0.48mol/L oxalic acid and 0.36mol/L
Hydrochloric acid mixed solution, 9mol/L hydrochloric acid solution, collect the solution of final step as the second solution to be measured；
3) chlorion of the second solution to be measured is removed
Take appropriate above-mentioned second solution to be measured to be put into polytetrafluoroethylene (PTFE) crucible, add appropriate concentrated nitric acid, in 160~180 DEG C of steamings
Dry, closeing the lid and be put into Muffle furnace 180 DEG C or so and be heated to solid crucible is disappeared, and 5% nitre is added in most backward crucible
Acid solution dilutes, you can obtains the simple titanium ion of matrix solution to be measured.
2. according to the method for claim 1, it is characterised in that the titanium dioxide is nano titanium oxide.
3. method according to claim 1 or 2, it is characterised in that in step 2), the oxalic acid for carrying out ion elution is molten
The dosage of liquid, oxalic acid and hydrochloric acid mixed solution and hydrochloric acid solution is respectively 5mL, 10mL and 20mL.
4. according to the method described in one of claim 1-3, it is characterised in that in step 2), described first taken is to be measured
The amount of solution is 0.2mL, and the amount of oxalic acid solution is 5mL.
5. according to the method described in one of claim 1-3, it is characterised in that in step 2), described first taken is to be measured
The amount of solution is 0.1mL, and the amount of oxalic acid solution is 5mL.
6. according to the method described in one of claim 1-4, it is characterised in that in step 2), in addition to anion exchange
The step of post cleans, the cleaning step includes：
Weigh AG1-X8 resin anion (R.A.)s 12-15g, ultra-pure water 16-20g is placed in beaker and mixes and place 12h, by anion tree
Fat mixed liquor, which is fitted into after anion-exchange column, sequentially adds ultra-pure water, HNO into anion-exchange column3, HCl, oxalic acid solution enter
Row cleaning.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710924209.0A CN107860639B (en) | 2017-09-30 | 2017-09-30 | Hydrofluoric acid-free titanium dioxide digestion and separation method |
Applications Claiming Priority (1)
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| CN117250253A (en) * | 2023-11-14 | 2023-12-19 | 中国计量科学研究院 | Method for measuring iron, copper and zinc in biological sample |
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