CN104459019B - A kind of method that detects free content of hydrochloric acid in titanium tetrachloride aqueous solution - Google Patents
A kind of method that detects free content of hydrochloric acid in titanium tetrachloride aqueous solution Download PDFInfo
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- CN104459019B CN104459019B CN201410771951.9A CN201410771951A CN104459019B CN 104459019 B CN104459019 B CN 104459019B CN 201410771951 A CN201410771951 A CN 201410771951A CN 104459019 B CN104459019 B CN 104459019B
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Abstract
The present invention relates to a kind of method that detects in titanium tetrachloride aqueous solution free content of hydrochloric acid, said method comprising the steps of: 1) under the protection of cold bath, with peristaltic pump by different volumes TiCl4Be driven in a certain amount of ultra-pure water, obtain variable concentrations TiCl4The aqueous solution; 2) use in NaOH standard liquid and TiCl4The aqueous solution, makes titration end-point pH value≤0.1,3) according to adding the total amount of NaOH standard liquid and the pH value of final solution to calculate former TiCl4The content of free HCl in the aqueous solution. Detection method provided by the invention is workable, quick, accurate, controls titration end-point pH value≤0.1 simultaneously, has avoided, because hydrolysis is to detecting the interference producing, having improved the accuracy of testing result, and testing result relative deviation is less than 4%.
Description
Technical field
The present invention relates to technical field of analytical chemistry, be specifically related to a kind of detection and analyze titanium tetrachloride aqueous solutionMethod, relates in particular to a kind of method that detects free content of hydrochloric acid in titanium tetrachloride aqueous solution.
Background technology
Titanium tetrachloride, chemical formula is TiCl4Inorganic compound, be produce Titanium and compound thereof importantIntermediate. At room temperature, TiCl4For colourless or micro-yellow liquid, belong to minority is liquid mistake in the time of room temperatureCross one of metal chloride, have compared with severe corrosive, irritant tart flavour.
TiCl4Unstable chemcial property, belongs to strong lewis acid, meeting and lewis base (even weak lewis base)Exothermic reaction generates adduct, therefore TiCl4Highly volatile and hydrolysis, TiCl4Liquid exposure is in airReact and produce a large amount of poisonous corrosivity smog with airborne moisture rapidly, run into water and can blastFormula reaction, first forms TiCl4·5H2O, finally generates hydrated titanium oxide solid (TiO2·xH2And salt O)Acid droplet mixture.
TiCl4Liquid, as the crucial intermediate products of the one in titanium industrial chain, is to produce titanium sponge and chloridising titaniumWhite primary raw material, about 90% TiCl4All be used to manufacture titanium dioxide pigment (TiO2), this process is mainlyTiCl4Hydrolysis. Due to TiCl4Liquid is very easily hydrolyzed, and can emit a large amount of white cigarettes in malaria,Therefore industrial titanium white production is generally first by TiCl4Liquid diluting becomes certain density TiCl4Aqueous solution conductStoring solution, is then hydrolyzed TiCl4The aqueous solution carries out next step. TiCl4The aqueous solution is by TiCl4Liquid addsA small amount of water obtains through hydrolysis, therefore in the aqueous solution, have free HCl, and the content of free HCl is to follow-upThe quality of producing titanium dioxide has material impact. So to TiCl4The accurate survey of free HCl content in the aqueous solutionMeasure particularly important.
TiCl4The configuration of the aqueous solution is the process of relative complex, and has certain risk. Normally at iceUnder the protection of water-bath, by TiCl4Liquid joins in cooling water or trash ice, and notes not adding TiCl4The mouth of pipe of liquid is deeply below liquid level, otherwise hydrolysate can stop up rapidly the mouth of pipe, causes configuration to complete.TiCl under this compound method4Hydrolysis acutely discharges a large amount of hydrochloric acid smog, operational hazards and cannot be quantitativeTiCl4Concentration of aqueous solution. Therefore controllably TiCl of a kind of safety, concentration4Aqueous solution compound method is extremely to haveNecessary.
At present, for TiCl4The determination method research of the aqueous solution is also fewer, the accurate instrument that the present age is advancedDevice analytical method is not suitable for TiCl yet4The detection analysis of aqueous solution utmost point acid system. Therefore finding one can examineCls analysis TiCl4The method of the aqueous solution, especially measures TiCl4The method pair of free HCl content in the aqueous solutionProduction in titanium dioxide is significant.
Summary of the invention
The object of the present invention is to provide a kind of method that detects titanium tetrachloride aqueous solution, particularly a kind of detectionThe method of free HCl content in titanium tetrachloride aqueous solution.
For reaching this goal of the invention, the present invention by the following technical solutions:
The invention provides a kind of TiCl of detection4In the aqueous solution, the method for free HCl content, comprises following stepRapid:
1) under ice-water bath protection, by TiCl4Liquid joins in ultra-pure water, and preparation obtains TiCl4Water-solubleLiquid;
2) neutralize with NaOH standard liquid;
3) neutralization is stablized after certain hour, controls titration end-point pH value≤0.1;
4) according to adding the total amount of NaOH standard liquid and the pH value of terminal solution, calculate TiCl4The content of free HCl in the aqueous solution.
Compound method concrete operation step of the present invention is: under ice-water bath protection, utilize peristaltic pump to incite somebody to actionTiCl4Liquid joins in ultra-pure water, adds TiCl at Xiang Shuizhong4Before liquid, first toward blowing air in water, withThe mouth of pipe that guarantee is submerged in water keeps dry, and precaution of hydrolysis product stops up the mouth of pipe, according to TiCl4Liquid is with superPure water proportioning difference, obtains the TiCl of variable concentrations4The aqueous solution.
Due to Ti4+The OH that precipitation consumes-Cannot determine, therefore cannot Measurement accuracy TiCl4Trip in the aqueous solutionFrom content of hydrochloric acid, the present invention, by controlling titration end-point pH value≤0.1, can effectively prevent Ti4+Precipitation is to surveyingThe interference that volume production is raw.
As optimal technical scheme, step 1 of the present invention) described TiCl4The volume proportion of liquid and ultra-pure waterFor 1:(0.2～15).
TiCl of the present invention4The volume proportion of liquid and ultra-pure water can be for example: 1:0.2,1:0.5,1:1、1:1.5、1:2、1:2.5、1:3、1:3.5、1:4、1:4.5、1:5、1:5.5、1:6、1:6.5、1:7、1:7.5、1:8、1:8.5、1:9、1:10、1:11、1:12、1:13、1:14、1:15。
As optimal technical scheme, step 1 of the present invention) TiCl that obtains of described preparation4Concentration of aqueous solution is0.5～4mol/L。
TiCl of the present invention4Concentration of aqueous solution can be for example 0.5mol/L, 1mol/L, 1.2mol/L,1.5mol/L、1.99mol/L、2.33mol/L、2.55mol/L、2.90mol/L、3.09mol/L、3.5mol/L、4mol/L。
As optimal technical scheme, step 2 of the present invention) concentration of described NaOH standard liquid is0.3～1mol/L。
The concentration of NaOH standard liquid of the present invention can be for example 0.3mol/L, 0.4mol/L,0.5mol/L、0.6mol/L、0.7mol/L、0.8mol/L、0.9mol/L、1mol/L。
As optimal technical scheme, step 3 of the present invention) described in and stabilization time be 10～90min, for exampleCan be 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min,90min。
As optimal technical scheme, step 3 of the present invention) described titration end-point pH value is 0.05～0.1.
Titration end-point pH value of the present invention can be for example 0.05,0.06,0.07,0.08,0.09,1.
Compared with prior art, the present invention has following beneficial effect:
1) the present invention prepares TiCl4The process gentleness of the aqueous solution, safety, can obtain the definite TiCl of concentration4The aqueous solution;
2) the present invention adopts acid-base titration to detect TiCl4Free HCl content in the aqueous solution, the method is simplePracticality, workable, quick and precisely; Avoid due to TiCl4Aqueous solution acidity is too high and be not suitable forThe modern precision such as ICP-MS, ICP-AES instrument detects the problem of analyzing;
3) the present invention adopts one-step method to detect TiCl4Free HCl content in the aqueous solution, compare adopt comprise heavyThe two-step method of shallow lake titanium ion detects, and measure error is less, the relative deviation control of sample detection result of the present inventionIn 3.04%;
4) control solution endpoint pH of the present invention is less than 0.1, can effectively shield Ti4+Hydrolysis, avoid it heavyForm sediment to the interference detecting;
5) the present invention has effectively coordinated research and development and improvement prepared by sulfuric acid process plus seed, for improving additional crystalline substancePlant the controllability of preparing and brought into play important function.
Detailed description of the invention
Further illustrate technical scheme of the present invention below by detailed description of the invention.
Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered asTo concrete restriction of the present invention.
The pH meter of using in the embodiment of the present invention is: plum Teller-Tuo benefit FE20; Measurement category is:0.00-14.00 (actual can measure-0.05); Certainty of measurement is: 0.01.
Embodiment 1
Get the TiCl that 5mL concentration is 1.99mol/L4The aqueous solution is placed in beaker; Dropwise slowly addThe NaOH standard liquid of 0.5mol/L, pH is surveyed with pH meter in dropping limit, limit, controls solution terminalPH value is less than 0.1, according to the amount of added NaOH standard liquid and solution endpoint pH, calculates formerTiCl4The content of free HCl in the aqueous solution; The same terms repeats to survey 3 groups and compares. Result of calculation is in table 1.
Table 1
As can be seen from Table 1, repeating to test the free hydrochloric acid content detecting for 3 of embodiment 1 times is respectively0.0304mol/L, 0.0323mol/L, 0.0315mol/L, as calculated, the relative deviation of its sample in measurement resultBe 3.04%.
Embodiment 2
Get the TiCl that 5mL concentration is 2.55mol/L4The aqueous solution is placed in beaker; Dropwise slowly addThe NaOH standard liquid of 0.5mol/L, pH is surveyed with pH meter in dropping limit, limit, controls solution terminalPH value is less than 0.1, according to the amount of added NaOH standard liquid and solution endpoint pH, calculates formerTiCl4The content of free HCl in solution; The same terms repeats to survey 3 groups and compares. Result of calculation is in table 2.
Table 2
As can be seen from Table 2, repeating to test the free hydrochloric acid content detecting for 3 of embodiment 2 times is respectively0.0409mol/L, 0.0433mol/L, 0.0417mol/L, as calculated, the relative deviation of its sample in measurement resultBe 2.91%.
Embodiment 3
Get the TiCl that 5mL concentration is 2.90mol/L4The aqueous solution is placed in beaker; Dropwise slowly addThe NaOH standard liquid of 0.5mol/L, pH is surveyed with pH meter in dropping limit, limit, controls solution terminalPH value is less than 0.1, according to the amount of added NaOH standard liquid and solution endpoint pH, calculates formerTiCl4The content of free HCl in the aqueous solution; The same terms repeats to survey 3 groups and compares. Result of calculation is in table 3.
Table 3
As can be seen from Table 3, repeating to test the free hydrochloric acid content detecting for 3 of embodiment 3 times is respectively0.0478mol/L, 0.0493mol/L, 0.0500mol/L, as calculated, the relative deviation of its sample in measurement resultBe 2.29%.
Embodiment 4
Get the TiCl that 20mL concentration is 0.5mol/L4The aqueous solution is placed in beaker; Dropwise slowly addThe NaOH standard liquid of 0.5mol/L, pH is surveyed with pH meter in dropping limit, limit, until add 5mLThe NaOH standard liquid of 0.5mo/L, stablizes after 40min, and recording pH is 0.09; According to addThe amount of NaOH standard liquid and solution endpoint pH, calculate former TiCl4In the aqueous solution, dissociate HCl'sContent is 1.14mol/L.
Embodiment 5
Get the TiCl that 10mL concentration is 2.33mol/L4The aqueous solution is placed in beaker; Dropwise slowly addThe NaOH standard liquid of 0.5mol/L, pH is surveyed with pH meter in dropping limit, limit, until add 51mLThe NaOH standard liquid of 0.5mo/L, stablizes after 28min, and recording pH is 0.00; According to addThe amount of NaOH standard liquid and solution endpoint pH, calculate former TiCl4In the aqueous solution, dissociate HCl'sContent is 7.6mol/L.
Embodiment 6
Get the TiCl that 5mL concentration is 3.09mol/L4The aqueous solution is placed in beaker; Dropwise slowly add 1mol/LNaOH standard liquid, pH is surveyed with pH meter in dropping limit, limit, until add 16mL1mo/L'sNaOH standard liquid, stablizes after 55min, and recording pH is 0.00; According to added NaOH markThe amount of accurate solution and solution endpoint pH, calculate former TiCl4In the aqueous solution, the content of free HCl is9.3mol/L。
Embodiment 7
Get the TiCl that 5mL concentration is 3.09mol/L4The aqueous solution is placed in beaker; Dropwise slowly addThe NaOH standard liquid of 0.3mol/L, pH is surveyed with pH meter in dropping limit, limit, until add 55mLThe NaOH standard liquid of 1mo/L, stablizes after 55min, and recording pH is 0.03; According to addThe amount of NaOH standard liquid and solution endpoint pH, calculate former TiCl4In the aqueous solution, dissociate HCl'sContent is 9.1mol/L.
Embodiment 8
Get the TiCl that 5mL concentration is 4mol/L4The aqueous solution is placed in beaker; Dropwise slowly add 0.5mol/LNaOH standard liquid, pH is surveyed with pH meter in dropping limit, limit, until add 38mL0.5mo/LNaOH standard liquid, stablize after 60min, recording pH is 0.08; According to added NaOHThe amount of standard liquid and solution endpoint pH, calculate former TiCl4In the aqueous solution, the content of free HCl is10.1mol/L。
Can find out from above-described embodiment 1-3, the relative deviation of sample detection result of the present invention can be controlled atIn 3.04%; Can find out from embodiment 4-8, at TiCl4When concentration of aqueous solution is 0.5～4mol/L, inspectionThe content that measures free hydrochloric acid in its solution is 1.14～10.1mol/L.
By embodiment 1-8, illustrate that the result relative deviation that detection method of the present invention obtains is less, and,Be less than 0.1 by controlling solution endpoint pH, effectively shielded Ti4+Hydrolysis, avoided its precipitation to inspectionThe interference of surveying, and can obtain quickly and accurately TiCl4Free HCl content in the aqueous solution.
Due to TiCl4The aqueous solution is important precursor liquid prepared by titanium dioxide plus seed, TiCl4Aqueous solution middle reachesWhen different from HCl content, the pattern on crystal seed, granular size, rutile content have impact, by thisThe detection method of invention, can conveniently control the content of the HCl that wherein dissociates to reach the condition of the optimum crystal seed of preparation,Industrial production is had to important using value.
Applicant's statement, the present invention illustrates process of the present invention by above-described embodiment, but the present inventionBe not limited to above-mentioned processing step, do not mean that the present invention must rely on above-mentioned processing step and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention is selected former to the present inventionThe selections of the equivalence replacement of material and the interpolation of auxiliary element, concrete mode etc., all drop on protection model of the present inventionWithin enclosing and disclosing scope.
Claims (6)
1. one kind is detected TiCl4In the aqueous solution, the method for free HCl content, is characterized in that, comprises followingStep:
1) under ice-water bath protection, utilize peristaltic pump by TiCl4Liquid joins in ultra-pure water, at Xiang ShuizhongAdd TiCl4Before liquid, first, toward blowing air in water, prepare and obtain TiCl4The aqueous solution;
2) neutralize with NaOH standard liquid;
3) neutralization is stablized after certain hour, controls titration end-point pH value≤0.1, to prevent Ti4+Precipitation is to surveyingThe interference that volume production is raw;
4) according to adding the total amount of NaOH standard liquid and the pH value of terminal solution, calculate TiCl4The content of free HCl in the aqueous solution.
2. the method for claim 1, is characterized in that step 1) described TiCl4Liquid is with superThe volume proportion of pure water is 1:(0.2～15).
3. method according to claim 1, is characterized in that step 1) described TiCl4The aqueous solutionConcentration is 0.5～4mol/L.
4. method according to claim 1, is characterized in that step 2) described NaOH standard is moltenThe concentration of liquid is 0.3～1mol/L.
5. method according to claim 1, is characterized in that: step 3) described in and stabilization timeBe 10～90min.
6. method according to claim 1, is characterized in that step 3) described titration end-point pHValue is 0.05～0.1.
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| CN102764601A (en) * | 2012-08-10 | 2012-11-07 | 杭州弗沃德精细化工有限公司 | Device and process for preparing titanium tetrachloride aqueous solution |
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| KR20020083652A (en) * | 2001-04-27 | 2002-11-04 | (주)아해 | Preparation of TiO2 fine powder from titanium tetrachloride with Alcohol or Acetone |
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| CN102764601A (en) * | 2012-08-10 | 2012-11-07 | 杭州弗沃德精细化工有限公司 | Device and process for preparing titanium tetrachloride aqueous solution |
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