CN106932528A - Method for analyzing molecular formula of ethoxy modified vanadium oxychloride catalyst - Google Patents
Method for analyzing molecular formula of ethoxy modified vanadium oxychloride catalyst Download PDFInfo
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- hydrolyzate
- ethyoxyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 29
- -1 ethoxy modified vanadium oxychloride Chemical class 0.000 title abstract description 10
- 238000004458 analytical method Methods 0.000 claims abstract description 18
- 229910001456 vanadium ion Inorganic materials 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- 239000000460 chlorine Substances 0.000 claims description 19
- 239000012895 dilution Substances 0.000 claims description 14
- 238000010790 dilution Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 9
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000004448 titration Methods 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 4
- 238000010168 coupling process Methods 0.000 claims description 4
- 238000005859 coupling reaction Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000295 emission spectrum Methods 0.000 claims description 4
- 230000001939 inductive effect Effects 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 230000003595 spectral effect Effects 0.000 claims description 3
- 239000003643 water by type Substances 0.000 claims description 3
- 241000370738 Chlorion Species 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 abstract description 4
- 125000005287 vanadyl group Chemical group 0.000 abstract description 2
- 239000000413 hydrolysate Substances 0.000 abstract 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 12
- 239000005060 rubber Substances 0.000 description 10
- 150000003681 vanadium Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 6
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- 239000000443 aerosol Substances 0.000 description 2
- PTXMVOUNAHFTFC-UHFFFAOYSA-N alumane;vanadium Chemical compound [AlH3].[V] PTXMVOUNAHFTFC-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 description 1
- 101710089042 Demethyl-4-deoxygadusol synthase Proteins 0.000 description 1
- 241001411320 Eriogonum inflatum Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910004688 Ti-V Inorganic materials 0.000 description 1
- 229910010968 Ti—V Inorganic materials 0.000 description 1
- 229910007727 Zr V Inorganic materials 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000012417 linear regression Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
- G01N21/68—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence using high frequency electric fields
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Catalysts (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to an analysis method of a molecular formula of an ethoxy modified vanadium oxychloride catalyst, which comprises the following steps: hydrolyzing the catalyst; concentration of chloride ion in catalyst hydrolysate]Measuring; vanadium ion concentration [ V ] in catalyst hydrolysate]Measuring; by the formula m ═ 3- [ Cl]/[V]Determining the molecular formula (EtO) of the ethoxy modified vanadium oxychloride catalyst to be testedmCl3-mVO. The method can accurately determine the ethoxy content in the ethoxy modified vanadyl chloride catalyst, the molecular formula of the obtained modified catalyst is close to the true value, and no forming method can determine the ethoxy content in the ethoxy modified vanadium catalyst at present.
Description
Technical field
The present invention relates to a kind of analysis method of ethoxyl content in vanadium series catalyst, more particularly to a kind of ethoxy
The analysis method of the modified chlorine vanadyl catalyst molecule formula of base.
Background technology
In the EP rubbers development of more than 40 years, the catalyst system and catalyzing of EP rubbers is constantly updated, from
The vanadium series catalyst and Titanium series catalyst of Ziegler-Natta (Z-N) catalyst system and catalyzing, to 90 years 20th century
The metallocene catalyst that grows up of generation, then to 21 century emerging non-metallocene catalyst.Catalyst is not
The disconnected direction towards high catalytic activity and high stability is gradually developed, make the performance of product and kind towards
More excellent direction is developed.
UCC companies of the U.S. are developed with SiO on gas-phase process2It is the basis of the vanadium series catalyst of carrier
On, the composite catalyst of Ti-V and Zr-V double activity center is developed, the composite catalyst can produce phase
To molecular vibrational temperature (Mw/Mn) curve in broad peak/bimodal polyethylene (PE) product.BP companies VC13
It is deposited on spherical MgC12On carrier be obtained vanadium series catalyst, with gas-phase process produce product not only
Mw/Mn (8~l0) is wider, and with preferable form, catalytic efficiency is also higher.Lukasz is equally used
Sol-gel process synthetic vectors, and supported V OC13Vanadium system PE catalyst is made, while using a chlorine two
Aluminium ethide modified catalyst, catalyst activity is carried to 25.8kg/mol by 7.8kg/mol.Russian Academy Of Sciences
The Bao Liesi Ke Fu catalyticing research spherical MgC1 of institute2It is vanadium series catalyst prepared by carrier, for slurry process
Vinyl polymerization, the polymer Mw/Mn of production is wide, melt flow rate (MFR) is adjustable, apparent density is high.
Ziegler-Natta type solution polymerization process is the conventional method for producing the minor official glue of second third, is that both can dissolve
Product, the homogeneous reaction carried out in the solvent that monomer and catalyst system are can dissolve again.Generally with linear paraffin
If n-hexane is solvent, vanadium oxytrichloride half as much again alkyl aluminium halide is catalyst, with hydrogen or other compounds
Used as molecular weight regulator, polymerization temperature is 30 DEG C~60 DEG C, and polymerization pressure is 0.4MPa~0.8MPa.
The main recovery by raw material preparations, polymerization, catalyst removal, monomer and solvent of technical process, refine, it is solidifying
The operation composition such as poly- and dry.Wherein typical manufacturer mainly has Dutch DSM N. V., the U.S.
ExxonMobil companies, Uniroyal companies of the U.S. (Lion companies of the Xian Ming U.S.), U.S. DuPont Dow
Elastomer company, Mitsui chemical company and Japan SYnthetic Rubber Co. Ltd etc..The production of each manufacturer
Technique differs from one another, wherein most typical representative is the solution polymerization process technique of DSM N. V., it is not only
Global maximum EP rubbers manufacturer, and it is poly- using solution in the device of Holland, Japan, Brazil etc.
Legal to be produced, its production capacity accounts for the 20% of world's solution polymerization process total productive capacity.
In recent years, DuPont Dow elastomers company developsTechnique successful Application industrially
For EP rubbers production brings important breakthrough.Technique uses metallocene as catalyst, highly concentrated
Synthesizing new EP rubbers in degree solution environmental.The technique is realized glues to relative molecular mass distribution, Mooney
The precise control of degree, ethene and ENB content, the rheological characteristic of rubber and curingprocess rate etc., so that
Realize the control to product uniformity.Polymerisation is carried out under the conditions of 120 DEG C, 3.4MPa.The work
Skill uses high temperature solution polymerization, uses the Titanocene catalyst system of constrained geometry, polymer quality
, up to 16.4%, catalyst residual quantity is considerably less in product for fraction, it is not necessary to which removing is processed, and invests low, produces
Product relative molecular mass distribution is narrow, and the length of polymer chain is uniform, and bulk density is small, and viscosity is high, DDGS
Content is low, can use sulfur cross-linking, external form when its molded mobility, tensile strength, calendering formation
The performances such as rate of extrusion when performance and extrusion molding are superior to traditional Ziegler-Natta types the third rubber of second
Sol solution polymerization technique, product Mooney range of viscosities is 20~45.
At present, the main initiator that EP rubbers synthesizer in the whole world is used has vanadium oxytrichloride, modified trichlorine
Vanadyl, metallocene.From polymerization methodses, due to efficiency of initiation, the difference of catalyst system and catalyzing, solution can be used
The modes such as polymerization, gas-phase polymerization.Jilin Petrochemical company EP rubbers device uses vanadium oxytrichloride to be catalyzed
Agent (abbreviation V- catalyst) and vanadium oxytrichloride add the ethyoxyl dichloro vanadyl that absolute ethyl alcohol reaction is prepared into urge
Agent (abbreviation Vx- catalyst), for producing straight chain EP rubbers product.
The content of the invention
Present invention aim at the analysis for providing a kind of modified chlorine vanadyl catalyst molecule formula of determination ethyoxyl
Method, this method can accurately determine the content of ethyoxyl in modified vanadium catalyst, so as to more be convenient to grind
Study carefully research of the catalyst to properties of product.
To realize the purpose of the present invention, the present invention discloses a kind of modified chlorine vanadyl catalyst molecule formula of ethyoxyl
Analysis method, including following process：
(1) hydrolysis of catalyst：
Chlorine vanadyl catalyst (EtO) that ethyoxyl is modifiedmCl3-mVO is slowly added under airtight condition
It is then closed to be kept for 30~120 minutes in 20~60mL deionized waters, obtain catalyst hydrolyzate；
(2) in catalyst in hydrolyzate chlorine ion concentration determination：
With phenolphthalein as indicator, gained catalyst hydrolyzate in step (1) is taken, use NaOH standard liquids
Titrated, the volume according to the NaOH standard liquids consumed when reaching titration end-point calculates catalysis
The concentration [Cl] of the chlorion in agent hydrolyzate；
(3) in catalyst in hydrolyzate vanadium ion concentration determination：
The another middle gained catalyst hydrolyzate of step (1) that takes is diluted, and obtains catalyst hydrolyzate dilution；
Using the ion of v element in inductive coupling plasma emission spectrograph measurement catalyst hydrolyzate dilution
Emission spectrum, according to its spectral intensity, with working curve method determine vanadium in catalyst hydrolyzate dilution from
Sub- concentration [V1]；According to extension rate, by the vanadium ion concentration [V in catalyst hydrolyzate dilution1] calculate
The vanadium ion concentration [V] gone out in catalyst hydrolyzate；
(4) determination of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl：
By the concentration [V] and chlorine of vanadium ion in the catalyst hydrolyzate of gained in step (2) and step (3)
The concentration [Cl] of ion calculates modified chlorine vanadyl catalyst molecule formula (EtO) of ethyoxylmCl3-mVO, wherein
The computing formula of m is m=3- [Cl]/[V].
The analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl of the present invention, wherein, step
(1) consumption of deionized water described in is preferably 20~40mL.
The analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl of the present invention, wherein, step
(1) time of closed holding described in is preferably 30~60 minutes.
The analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl of the present invention, wherein, step
(2) sampling amount of catalyst hydrolyzate described in is preferably 10mL.
The analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl of the present invention, is preferably applied to
The analysis of modified vanadium oxytrichloride catalyst molecule formula, further preferably urges suitable for alkoxy-modified vanadium oxytrichloride
The analysis of agent molecular formula.
The present invention has the advantages that：(1) ethyoxyl contains in can accurately determining modified vanadium catalyst
Amount；(2) the modified catalyst molecular formula for being drawn by the present invention is close to actual value；(3) currently without one
The method of kind shaping can determine the ethoxyl content in modified vanadium catalyst.
Brief description of the drawings
Fig. 1 is the working curve of the concentration of vanadium ion in determination catalyst hydrolyzate dilution in embodiment 1
Figure.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is premised on technical solution of the present invention
Under implemented, give detailed implementation method and process, but protection scope of the present invention be not limited to it is following
Embodiment, the technological parameter of unreceipted actual conditions in the following example, generally according to normal condition.
Embodiment 1：
20mL deionized waters are moved into through nitrogen so that the speed of 20r/s is slow with peristaltic pump at ambient temperature
Process and in closed 150mL triangular flasks, it is to be measured modified to extract 0.5mL with the syringe through dried process
Vanadium catalyst, is slowly dropped in the triangular flask equipped with deionized water, and time for adding was controlled at 1~2 minute
It is interior, with the carrying out being added dropwise, white haze rise is had in triangular flask, white haze is to dissociate the HCl gases for coming,
But continuity over time, HCl gases can be absorbed to form hydrochloric acid solution by deionized water, liquid table is observed
The aerosol situation in face, will now keep closed good.After 20min, exist without visual aerosol in bottle, now
Bottle stopper is opened, during hydrolyzate moved into 250mL volumetric flasks, constant volume is standby.
0.01mol/mL NaOH standard liquids, addition are added in alkaline buret>30mL, static reserve.
Then the modified vanadium catalyst hydrolyzates of 10mL are removed from above-mentioned 250mL volumetric flasks with 10mL pipettes,
It is placed in iodine flask, it is standby, so repeat to take out 3 hydrolyzate samples, to ensure the collimation of titration.
To 1 drop phenolphthalein solution is separately added into three iodine flasks, left hand controls the flow of alkali lye, and the right hand is gently
Shake iodine flask, to ensure the harmony of acid-base reaction.When pink colour is shown slightly in iodine flask, stop titration,
Bottle is shaken gently for, treats that pink colour disperses, then instill half drop alkali lye, be shaken gently for bottle, and rushed with distilled water
Pink colour disperses quickly in brush bottle wall, such as bottle, continues to instill half drop alkali lye, repeats aforesaid operations, treats powder in bottle
When color can not disperse completely, indicate that terminal has been arrived in this titration, write down the alkali lye consumption of consumption, such as table 1
It is shown.
The titration data table of table 1
The preparation of standard liquid：3 100mL volumetric flasks are taken, as shown in table 2, aluminium vanadium is separately added into and is mixed
Standardization solution (wherein vanadium ion concentration is (100 ± 1mg/L)), and 100mL is settled to respectively,
It is stand-by and be settled to 100mL respectively, it is stand-by.
The standard liquid of table 2
| Aluminium vanadium mixed standard solution volume V/mL | Correspondence vanadium ion concentration/(μ g/mL) |
| 1.0 | 1 |
| 5.0 | 5 |
| 10 | 10 |
The drafting of working curve：Inductive coupling plasma emission spectrograph is lighted a fire after start preheating 4h,
Stabilization 30min, rectifies an instrument, and instrument is adjusted to optimum Working, selects element to be measured and analysis wavelength,
The μ g/mL (water) of sequential determination 0；1.0μg/mL；5.0μg/mL；10 μ g/mL standard liquids, with vanadium from
Sub- concentration is abscissa (unit：μ g/mL), corresponding the intensity of spectral line be ordinate, drawing curve,
Its equation of linear regression is [V1] '=6.163479 × 10-3× I-0.1025682, linearly dependent coefficient
R=0.99999, wherein [V1] ' is the vanadium ion concentration (unit in solution to be measured：μ g/mL), I is catalysis
The intensity of emission spectra that agent hydrolyzate dilution is measured.
It is another to take catalyst hydrolyzate 1mL, and diluted 1000 times, catalyst hydrolyzate dilution is obtained,
Catalyst hydrolyzate is determined while using inductive coupling plasma emission spectrograph drawing curve
The v element emission spectrum of dilution.The vanadium in catalyst hydrolyzate dilution can be obtained according to working curve
Ion concentration [V1] ' (unit：μ g/mL), its unit is converted, obtain catalyst hydrolyzate dilution
Middle vanadium ion concentration [V1] (unit：Mol/L it is) 1.76 × 10-6mol/L.According to formula [V]=1000 [V1],
The concentration [V] for calculating vanadium ion in catalyst hydrolyzate is 1.76 × 10-3mol/L。
By the molecular formula (EtO) of the chlorine oxygen alkane catalyst that is modifiedmCl3-mVO draws the calculating of following ethoxyl content
Formula：
M=3- [Cl]/[V]
The concentration of vanadium ion, mol/L wherein in [V]-above-mentioned catalyst hydrolyzate；
Chlorine ion concentration in [Cl]-above-mentioned catalyst hydrolyzate, mol/L；
It is 1.26 to calculate the value of m, and the accurate formula for drawing catalyst to be measured is (EtO)1.25Cl1.75VO。
Claims (5)
1. a kind of analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl, including following process：
(1) hydrolysis of catalyst：
Chlorine vanadyl catalyst (EtO) that ethyoxyl is modifiedmCl3-mVO is slowly added under airtight condition
It is then closed to be kept for 30~120 minutes in 20~60mL deionized waters, it is transferred to 250mL volumetric flasks
In, constant volume obtains catalyst hydrolyzate；
(2) in catalyst hydrolyzate chlorine ion concentration measure：
With phenolphthalein as indicator, gained catalyst hydrolyzate in step (1) is taken, use NaOH standard liquids
Titrated, the volume according to the NaOH standard liquids consumed when reaching titration end-point calculates catalysis
The concentration [Cl] of the chlorion in agent hydrolyzate；
(3) in catalyst hydrolyzate vanadium ion concentration measure：
The another middle gained catalyst hydrolyzate of step (1) that takes is diluted, and obtains catalyst hydrolyzate dilution；
Using the ion of v element in inductive coupling plasma emission spectrograph measurement catalyst hydrolyzate dilution
Emission spectrum, according to its spectral intensity, with working curve method determine vanadium in catalyst hydrolyzate dilution from
Sub- concentration [V1]；According to extension rate, by the vanadium ion concentration [V in catalyst hydrolyzate dilution1] calculate
Go out vanadium ion concentration [V] in catalyst hydrolyzate；
(4) determination of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl：
By the concentration [V] and chlorine of vanadium ion in the catalyst hydrolyzate of gained in step (2) and step (3)
The concentration [Cl] of ion calculates modified chlorine vanadyl catalyst molecule formula (EtO) of ethyoxylmCl3-mVO, wherein
The computing formula of m is m=3- [Cl]/[V].
2. the analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl as claimed in claim 1,
Characterized in that, the consumption of deionized water described in step (1) is 20~40mL.
3. the analysis side of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl as claimed in claim 1 or 2
Method, it is characterised in that the time of closed holding described in step (1) is 30~60 minutes.
4. the analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl as claimed in claim 1,
Characterized in that, the sampling amount of catalyst hydrolyzate described in step (2) is 10mL.
5. the analysis method of the modified chlorine vanadyl catalyst molecule formula of ethyoxyl as claimed in claim 3,
Characterized in that, the sampling amount of catalyst hydrolyzate described in step (2) is 10mL.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511021474.5A CN106932528A (en) | 2015-12-31 | 2015-12-31 | Method for analyzing molecular formula of ethoxy modified vanadium oxychloride catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511021474.5A CN106932528A (en) | 2015-12-31 | 2015-12-31 | Method for analyzing molecular formula of ethoxy modified vanadium oxychloride catalyst |
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| CN106932528A true CN106932528A (en) | 2017-07-07 |
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| CN201511021474.5A Pending CN106932528A (en) | 2015-12-31 | 2015-12-31 | Method for analyzing molecular formula of ethoxy modified vanadium oxychloride catalyst |
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Cited By (1)
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| CN111830197A (en) * | 2020-07-14 | 2020-10-27 | 宁波拓烯新材料科技有限公司 | Method for analyzing composition of chlorine-containing vanadium compound |
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