CN1085677C - Method for removing large amount of organic impurities from titanium tetrachloride - Google Patents
Method for removing large amount of organic impurities from titanium tetrachloride Download PDFInfo
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- CN1085677C CN1085677C CN98101540A CN98101540A CN1085677C CN 1085677 C CN1085677 C CN 1085677C CN 98101540 A CN98101540 A CN 98101540A CN 98101540 A CN98101540 A CN 98101540A CN 1085677 C CN1085677 C CN 1085677C
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- Prior art keywords
- anhydrous
- large amount
- organic impurities
- titanium tetrachloride
- ticl
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- 238000000034 method Methods 0.000 title claims abstract description 86
- 239000012535 impurity Substances 0.000 title claims abstract description 69
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 53
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 66
- 239000002994 raw material Substances 0.000 claims abstract description 51
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 28
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005049 silicon tetrachloride Substances 0.000 claims abstract description 27
- 238000001577 simple distillation Methods 0.000 claims description 53
- 238000010992 reflux Methods 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 17
- 238000012545 processing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 8
- -1 polyethylene Polymers 0.000 abstract description 13
- 238000011084 recovery Methods 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000000746 purification Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 8
- 239000004698 Polyethylene Substances 0.000 abstract description 6
- 239000004743 Polypropylene Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 229920000573 polyethylene Polymers 0.000 abstract description 6
- 229920001155 polypropylene Polymers 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 229910003074 TiCl4 Inorganic materials 0.000 abstract 3
- 239000002699 waste material Substances 0.000 abstract 3
- 239000012153 distilled water Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000009835 boiling Methods 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000004821 distillation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000013094 purity test Methods 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to a method for purification of titanium tetrachloride, more specifically to a method for removing a large quantity of organic substance impurities from waste TiCl4 which is used in the process of manufacture of a polyethylene catalyst and a polypropylene catalyst. The method of the present invention is characterized in that one compound of anhydrous silicon tetrachloride, anhydrous iron trichloride and anhydrous aluminum trichloride is added into the raw material of the waste TiCl4 to be heated, and then, the mixture back flows to be distilled. The method of the present invention has the advantages of less equipment investment, simple technology and low recovery cost of TiCl4, and the waste titanium tetrachloride can be circularly used.
Description
One, technical field
The present invention relates to the to purify technology of titanium tetrachloride is said so more specifically and remove large amount of organic impurities in the used useless titanium tetrachloride from the process of making polyethylene and polypropylene catalyst, and makes TiCl
4The method that obtains purifying.
Two, background technology
In the process of making polyethylene and polypropylene catalyst, use TiCl
4As reaction medium and washing composition.The titanium tetrachloride consumption is few in above-mentioned process.But, used TiCl
4Polluted by large amount of organic, wherein organic impurities content can be up to about 15%.This TiCl that contains large amount of organic impurities
4Can not reuse again in the return catalizer manufacturing.Therefore, the factory of more domestic manufacturing polyethylene and polypropylene catalyst have to be with these useless TiCl
4Store pending.So make the useless TiCl that stores in the factory of polyethylene and polypropylene catalyst
4Increase year by year, the factory that has has stored and has reached thousands of tons of, and this is not only loss economically, and is a serious potential safety hazard.
Both at home and abroad to this TiCl that contains large amount of organic impurities
4Purification research still rare.Adopt common distillation method a large amount of organic impurities can not be separated removes at all.At present, the domestic factory that has once adopted the common rectification method TiCl that gives up
4Purification, and the TiCl after purifying
4The purity of product only is 94～95%.Through remaining in TiCl after the above-mentioned conventional distillation purification
4In organic impurities be some highly stable compounds, some compounds wherein also with TiCl
4Form compound, the organic impurities that has when heating is difficult to the carbonization that is decomposed.And the boiling point and the TiCl of the compound that when making catalyzer, is added
4Boiling point close, for example, the equal and TiCl of No. 200 gasoline (boiling range 140-200 ℃) that added when making catalyzer and octanol (194.5 ℃)
4Boiling point (136 ℃) is close, so adopt common rectification method to be difficult to these organic impurities are removed.
Beijing technical concern company limited is the specialized company that makes polyolefin catalyst, and need use TiCl every year
4About 500 tons, make the used TiCl of catalyzer
4Its purity about 84%.In order to solve TiCl
4Recycle problem in making the catalyzer process has adopted the conventional distillation device to remove lower boiling and high boiling organic impurities, the TiCl after the purification
4Product purity is 94～95%, and it is 94～95% TiCl that product purity after the purification was once attempted to utilize by the said firm
4A certain proportion of technical pure TiCl arranges in pairs or groups
4Be used to make polyolefin catalyst, experiment shows catalyzer generation detrimentally affect.
European patent EP 0343901 has been reported and reclaimed the method for high purity toluene, hexane, titanium tetrachloride, tetrahydrofuran (THF) and used equipment thereof from the mixture of toluene, hexane, titanium tetrachloride.This method is to add complexing agent earlier in containing the mother liquor that has two kinds of close liquid of boiling point at least, a kind of liquid in the mixing liquid and a kind of complexing agent form the precipitation and complexation thing, from mother liquor, be settled out precipitated complex compound, from residual mother liquor, reclaim second kind of liquid.Above-mentioned two kinds of liquid substances are tetrahydrofuran (THF) and toluene, and complexing agent is a titanium tetrachloride, and sedimentary complex compound is TiCl
42C
4H
8O or TiCl
4C
4H
8O.From residual liquid, reclaim toluene, hexane, titanium tetrachloride and tetrahydrofuran (THF) a kind of compound wherein with the highly efficient distilling method.Might obtain the higher titanium tetrachloride of purity with above-mentioned highly efficient distilling method.But the used facility investment of the highly efficient distilling method of this method is big, the technical process complexity.If only reclaim hundreds of ton TiCl every year
4Industrial scale, the highly efficient distilling equipment that uses investment like this obviously is unfavorable.
Three, summary of the invention
It is little that purpose of the present invention just is to work out the simple investment of a kind of equipment used, the chemical process of removing large amount of organic impurities from titanium tetrachloride.
A kind of method of removing large amount of organic impurities from titanium tetrachloride of the present invention is containing the TiCl of large amount of organic impurities
4Raw material in add for the first time anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of compound wherein, carrying out reflux handles, heat treated is carried out simple distillation or rectifying after refluxing, the titanium tetrachloride product that distillation or rectifying go out to obtain purifying, can remove organic impurities a large amount of in the raw material titanium tetrachloride like this, make TiCl
4Obtain to purify.
Test shows and is containing the TiCl of large amount of organic impurities
4Behind the silicon tetrachloride of middle adding sufficient quantity, FERRIC CHLORIDE ANHYDROUS, the aluminum trichloride (anhydrous) a kind of compound wherein, organic impurities when carrying out the reflux processing in the titanium tetrachloride separates out very soon, after the reflux processing through suitable for some time, distill again, titanium tetrachloride is distilled.The TiCl of the purification that is obtained
4The density of product is than raw material TiCl
4Density increase.
The TiCl that contains organic impurities
4The measuring method of purity be the problem that must solve.Contain organic impurities TiCl
4The mensuration of purity is problem of difficulty.The present chemical analysis that uses, because sampling error is big, can only be as a kind of householder method of reference.
Be dissolved in TiCl based on organic impurities
4After make it painted, can check TiCl qualitatively with colorimetry
4The content of middle organic impurities.With what of chrominance representation organic impurities content, the big foreign matter content height of colourity, otherwise organic impurities content is low.But this method is not a kind of quantitative methods, especially for containing the many TiCl of organic impurity
4It is just more difficult to use this method; And because organic impurity makes TiCl
4Painted very sensitive, contain the TiCl of the organic impurity of ppm
4Also can make it painted medium-term and long-term placement of air.So colorimetry also can only be as the auxiliary method of inspection of a kind of reference.Said colourity is to be the colorimetric standard specimen with the potassium bichromate solution, contains what milligram K with every liter
2Cr
2O
7Represent.
Based on organism and TiCl
4The bigger principle of density difference, adopt densitometer method can determine TiCl
4Purity.This method is compared with chemical analysis, has favorable reproducibility, the advantage that error is little, the very little TiCl of inorganic impurity for containing a large amount of organic impuritys
4, this is a kind of method of measuring purity more accurately and reliably.The main densitometer method that adopts of this test is determined TiCl
4Purity, and as a reference with colorimetry.Under a certain temperature, measure and contain organic impurity TiCl
4Density, then can obtain with respect to pure TiCl
4Relative density (representing) with %, the supposition organic impurities density then can obtain TiCl
4Purity.Because the density of organic impurities supposes, so the TiCl that obtains with this method
4Purity and actual value have certain error, and this error is with TiCl
4The raising of purity and reducing.As seen, this method is used to contain the high-purity Ti Cl of a small amount of organic impurity
4Purity testing, be method more accurately at present.Said relative density is pure TiCl under the density value of measuring under a certain temperature and this temperature
4The ratio of density value.Said like this TiCl
4Purity be the supposition organic impurities density be 0.9g/cm
3Condition under, the TiCl that comes out by the density calculation of measuring
4Percentage composition.
In method of removing a large amount of organic impuritys from titanium tetrachloride of the present invention, used raw material contains in the titanium tetrachloride of large amount of organic impurities, to contain the TiCl of 75～98% weight
4For good, again to contain the TiCl of 84～95% weight
4For better.Containing the TiCl of large amount of organic impurities
4Raw material in add for the first time anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, the weight of aluminum trichloride (anhydrous) a kind of compound wherein is the 0.1-6% that contains the titanium tetrachloride material quantity of large amount of organic impurities, if its add-on is less than 0.1%, the effect of removing organic impurities is bad, if its add-on strengthens purification TiCl greater than 6%
4Cost, be that the 0.5-2% that contains the titanium tetrachloride material quantity of large amount of organic impurities is good so add for the first time the weight of wherein a kind of anhydrous compound of anhydrous silicon tetrachloride, iron trichloride, aluminum chloride.
After adding anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of anhydrous compound wherein, carry out reflux and handle, the temperature that its reflux is handled is 70～150 ℃, carries out reflux with 100-150 ℃ again and is treated to good.The time that reflux is handled is 0.1～6 hour, again with 1-4 hour for well.After reflux is finished dealing with, carrying out simple distillation again under 130-155 ℃ temperature, is good to carry out simple distillation under 136-148 ℃ temperature again.
Through adding anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of anhydrous compound wherein, when reflux was handled, organic impurities was separated out very soon, TiCl
4In organism issue estranged separating or carbonization in the effect or the catalysis of above-mentioned anhydrous chloride, generate some low-boiling compounds and overflow, after handling through the reflux of one section suitable time, its simple distillation is come out.But the TiCl that is obtained
4Distillage produces dregs sometimes, contains the small amount of solid state suspended substance.This suspended substance may be anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of anhydrous chloride and the TiCl wherein that is added
4In the reaction of some organic impurities form, under the room temperature at TiCl
4Middle solubleness is little, exists and be suspended state.In order to remove the suspended substance in the product, make TiCl
4Product is more as clear as crystal, can adopt any method in two kinds of following methods to handle and remove TiCl
4In suspended solid.
First method is through adding anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of compound wherein the above-mentioned first time, reflux is handled, the product that carries out simple distillation or rectifying is raw material (claiming system product just again), the water that in raw material, adds sufficient quantity, carry out simple distillation or rectifying again, generate the as clear as crystal higher TiCl of purity
4Product, the colourity of this product also decreases, and the distillatory temperature is 130-155 ℃ when carrying out simple distillation again, again to carry out redistillation under 136～148 ℃ the temperature for well.The water that is added is good with distilled water, deionization a kind of water wherein, the water yield that is added is good with the 10-20% that adds their a kind of anhydrous compound weight wherein again for 1～20% of the anhydrous silicon tetrachloride that adds for the first time, FERRIC CHLORIDE ANHYDROUS, wherein a kind of anhydrous chloride weight of aluminum trichloride (anhydrous).If the water yield that added is greater than 20%, TiCl
4Loss amount increase TiCl
4The rate of recovery reduce.
Second method is through adding anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of compound wherein the above-mentioned first time, after reflux is handled, add for the second time anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of compound wherein, after carrying out the reflux processing second time, carry out simple distillation, in the product that simple distillation obtains, add the water of sufficient quantity, carry out the simple distillation second time, and obtain as clear as crystal, the TiCl that purity is higher
4Product.Add for the second time anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, the weight of aluminum trichloride (anhydrous) a kind of compound wherein is to contain 0.05～1.5% of large amount of organic impurities titanium tetrachloride material quantity, the temperature of carrying out reflux for the second time is 70～150 ℃, be good with 100-150 ℃ again, the time that reflux is handled is 0.1～2 hour, the water yield that is added is the anhydrous silicon tetrachloride of the first time and the adding second time, FERRIC CHLORIDE ANHYDROUS, 1～20% of wherein a kind of anhydrous chloride gross weight of aluminum trichloride (anhydrous) is the first time with the water yield that adds again, the anhydrous silicon tetrachloride that add the second time, FERRIC CHLORIDE ANHYDROUS, the 10-20% of wherein a kind of anhydrous chloride gross weight of aluminum trichloride (anhydrous) is good.The temperature of carrying out simple distillation for the second time is 130-155 ℃, carries out the simple distillation second time for well with 136～148 ℃ again.
In technological process of the present invention, adding anhydrous silicon tetrachloride, iron trichloride, aluminum chloride a kind of anhydrous chloride wherein, reflux is handled, and carries out simple distillation, distills out TiCl
4Raffinate behind the product (comprising raffinate) accounts for about the 4-5% of raw material weight, raffinate can be poured out from matrass, a small amount of black adhesive is arranged at the bottom of bottle, through adding the content of anhydrous silicon tetrachloride in the product that distillation draws behind the water, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of anhydrous chloride wherein, chemical analysis results shows＜0.005%.Add the residual amount that is produced after the water treatment and be about 10 times of the weight that adds entry.The TiCl that is contained in all raffinate and the residue in commerical test and in producing
4All can reclaim again and handle TiCl
4The rate of recovery be expected further raising.
Used equipment is matrass or still kettle and rectifying tower in technology of the present invention.The working method of rectifying tower is the method that affiliated those of ordinary skills all know.
Advantage of removing the method for large amount of organic impurities from titanium tetrachloride of the present invention is:
1. technical process of the present invention and equipment used are simple, and facility investment is little, are a kind of simple and economical method, product with low cost.
2. can the TiCl of large amount of organic impurities will be contained with technology of the present invention
4Purification reaches or near technical pure TiCl
4Purity, TiCl
4Rate of recovery height, the TiCl after the purification
4Can realize TiCl in the catalyzer manufacturing processed fully
4Recycle, improved the quality of making polyethylene and polypropylene catalyst product, reduced the manufacturing catalyst production cost.
Four, specific embodiment
Below with embodiment method of removing large amount of organic impurities from titanium tetrachloride of the present invention is further described, will help method of the present invention and advantage thereof are done further to understand.Protection scope of the present invention is not subjected to the qualification of these embodiment, and protection scope of the present invention is limited by claims.
Embodiment 1
Add raw material 200 grams in matrass, used raw material directly adopts makes the titanium tetrachloride that the catalyzer exhausted contains large amount of organic impurities, raw material TiCl
4In contain the TiCl of 84.88% weight
4, colourity＞105, the weight of the aluminum trichloride (anhydrous) that adds for the first time in raw material is 1.5% of material quantity, carrying out the reflux processing under 136 ℃ ± 4 ℃ the temperature after 2.5 hours, carries out simple distillation under 142 ± 6 ℃ temperature, its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＞1,000 1.608 (19 ℃) 93.01 91.84
TiCl
4The rate of recovery be 96%.
Embodiment 2
Its working method and used equipment is substantially with embodiment 1, and the weight of the aluminum trichloride (anhydrous) that only different is is added is 2.0% of raw material weight, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＞1,000 1.63 (17.5 ℃) 94.14 93.26
TiCl
4The rate of recovery be 95.6%.
Embodiment 3
Its working method and used equipment is substantially with embodiment 1, and the weight of the aluminum trichloride (anhydrous) that only different is is added is 3.0% of raw material weight, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＞100 1.634 (19 ℃) 94.52 93.70
TiCl
4The rate of recovery be 95.1%.
Embodiment 4
Its working method and used equipment is substantially with embodiment 1, and the weight of the aluminum trichloride (anhydrous) that only different is is added is 4.0% of raw material weight, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＞100 1.636 (19 ℃) 94.63 93.84
Embodiment 5
Its working method and used equipment is substantially with embodiment 1, and only different is, and what to be added is FERRIC CHLORIDE ANHYDROUS, consequently TiCl
4Purity be 91.90%, TiCl
4The rate of recovery be 95.7%.
Embodiment 6
Its working method and used equipment is substantially with embodiment 1, and only different is, and what to be added is anhydrous silicon tetrachloride, consequently TiCl
4Purity be 91.70%, TiCl
4The rate of recovery be 95.3%.
Embodiment 7
Add raw material 200 grams in matrass, used raw material is the titanium tetrachloride that contains large amount of organic impurities, contains TiCl in the raw material
494.86% (makes the TiCl that the catalyzer exhausted contains large amount of organic impurities
4Purify through rectification method), the weight that adds for the first time aluminum trichloride (anhydrous) in raw material is 0.5% of raw material weight, carrying out the reflux processing under 136 ℃ ± 2 ℃ the temperature after 2.5 hours, under 137 ℃ ± 5 ℃ temperature, carry out simple distillation, its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＞100 1.668 (22 ℃) 96.76 96.35
TiCl
4The rate of recovery be 96.3%.
Embodiment 8
Its working method and used equipment is substantially with embodiment 7, and the weight of the aluminum trichloride (anhydrous) that only different is is added is 0.75% of raw material weight, and the time that reflux is handled is to carry out simple distillation after 1 hour, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＜500 1.664 (20 ℃) 96.35 96.01
Embodiment 9
Its working method and used equipment is substantially with embodiment 7, and the weight of the aluminum trichloride (anhydrous) that only different is is added is 0.75% of raw material weight, and the time that reflux is handled is carried out simple distillation after being 2.5 hours, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＜100 1.696 (20 ℃) 98.2 98.05
Embodiment 10
Its working method and used equipment is substantially with embodiment 7, and the weight of the aluminum trichloride (anhydrous) that only different is is added is 1.0% of raw material weight, and the time that reflux is handled is carried out simple distillation after being 2.5 hours, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＜50 1.710 (20 ℃) 99.02 98.95
Embodiment 11
Its working method and used equipment is substantially with embodiment 7, and the weight of the aluminum trichloride (anhydrous) that only different is is added is 1.1% of raw material weight, and the time that reflux is handled is carried out simple distillation after being 2.5 hours, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＜50 1.710 (20 ℃) 99.02 98.95
Embodiment 12
Its working method and used equipment is substantially with embodiment 7, and the weight of the aluminum trichloride (anhydrous) that only different is is added is 1.2% of raw material weight, and the time that reflux is handled is carried out simple distillation after being 2.5 hours, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＜100 1.70 (23 ℃) 98.71 98.60
Embodiment 13
Its working method and used equipment is substantially with embodiment 7, and the weight of the aluminum trichloride (anhydrous) that only different is is added is 1.6% of raw material weight, and the time that reflux is handled is carried out simple distillation after being 2.5 hours, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＜40 1.712 (21 ℃) 99.22 99.16
Embodiment 14
Its working method and used equipment is substantially with embodiment 7, and the weight of the aluminum trichloride (anhydrous) that only different is is added is 2.0% of raw material weight, and the time that reflux is handled is carried out simple distillation after being 4 hours, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＜50 1.734 (10 ℃) 99.36 99.31
Embodiment 15
In matrass, fill with after adding for the first time aluminum trichloride (anhydrous) (weight of the aluminum trichloride (anhydrous) that is added be material quantity 1.2%), reflux was handled after 2.5 hours, through colourity＜100 that simple distillation obtained, titanium tetrachloride 200 grams of relative density 98.71% are as for the second time pending raw material, to for the second time pending TiCl
4Add distilled water in the raw material, the amount of the distilled water that is added is carried out the simple distillation second time for 17.8% of the aluminum trichloride (anhydrous) weight that added for the first time under 136 ± 6 ℃ temperature, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＜50 1.71 (23 ℃) 99.29 99.21
Pure TiCl after handling for the second time
4The rate of recovery be 94.6%.
Embodiment 16
Its working method and used equipment are substantially with embodiment 15, the weight that only different is adds aluminum trichloride (anhydrous) for the first time is 1.6% of material quantity, after the reflux 2.5 hours, through simple distillation colourity＜50, titanium tetrachloride 200 grams of relative density 99.12% are as for the second time pending TiCl
4Raw material adds distilled water in raw material, the amount of the distilled water that is added is 19.2% of the aluminum trichloride (anhydrous) weight that added for the first time, and its result is as follows:
The quality colourity density (g/cm of simple distillation product
3) relative density % TiCl
4Purity, %＜30 1.714 (19 ℃) 99.14 99.06
Embodiment 17
With method and condition, add aluminum trichloride (anhydrous), colourity＞1000 that obtained after the simple distillation again after reflux is handled, TiCl through embodiment 2
4Product 550 grams of purity 93.26% are raw material, in above-mentioned 550 gram raw materials, add distilled water, the weight of the distilled water that is added is 10% of the aluminum trichloride (anhydrous) weight that added for the first time, in the glass filler tower, carry out rectifying, carry out distillation operation by the working method that affiliated technical field those of ordinary skill is known, used glass filler tower Φ 30 * 450mm, filler Φ 3 * 9mm porcelain ring, bed stuffing height 400mm, the distillate quality and quantity that rectifying obtained is listed in the table 1.
Table 1 rectifying product amount and quality index numbering product amount colourity density relative density purity
(g) (g/cm
3) (%) (TiCl
4%) 9-1* 95＜60 1.57, (18 ℃) 90.72 88.929-2 105＜50 1.72, (17.5 ℃) 99.34 99.279-3 105＜50 1.722, (17.5 ℃) 99.45 99.409-4 100＜50 1.716, (17 ℃) 99.05 98.979-5 90＜70 1.714, (18 ℃) 99.04 98.95 residue liquid 40＞10000---9-1* annotated for containing lower boiling cut.
Embodiment 18
Add raw material 500 grams in matrass, used raw material contains the TiCl that large amount of organic is purified through the conventional distillation method for making the catalyzer exhausted
4, raw material TiCl
4In contain TiCl
494.86%.In above-mentioned raw material, add aluminum trichloride (anhydrous) for the first time, the weight of the aluminum trichloride (anhydrous) that is added is 1.7% of material quantity, carrying out the reflux processing under 136 ± 2 ℃ the temperature after 2.5 hours, under 136 ℃ ± 5 ℃ temperature, carry out simple distillation, obtain colourity＜20, the TiCl of relative density 99.23%
4, to colourity＜20, the TiCl of relative density 99.23%
4In add distilled water, the amount of the distilled water that is added is 15% of the aluminum trichloride (anhydrous) amount that added for the first time, knows all that with those of ordinary skill in the field working method carries out rectifying again.Used rectifying tower is Φ 30 * 450mm during rectifying, filler Φ 3 * 9mm porcelain ring, bed stuffing height 400mm, low boiler cut accounts for about 10% of raw material, relative density 97.55%, product cut accounts for raw material about 85%, and the still raffinate accounts for about 5% of raw material, and the quality of product is as follows: colourity density (g/cm
3) relative density % TiCl
4Purity %＜10 1.732 (16.8 ℃) 99.96 99.95
Embodiment 19
Its working method and used equipment is substantially with embodiment 18, and the weight of the only different aluminum trichloride (anhydrous)s that are in raw material to be added is 2.0% of material quantity, reflux 3 hours, the TiCl that is obtained
4Be colourity＜30, the TiCl of relative density 99.31%
4, to colourity＜30, the TiCl of relative density 99.31%
4In add distilled water, the amount of the distilled water that is added is carried out rectifying for 15% of the aluminum trichloride (anhydrous) weight that added for the first time, the quality of product is as follows: colourity density (g/cm
3) relative density % TiCl
4Purity %＜10 1.730 (16 ℃) 99.75 99.73
Embodiment 20
Add raw material 200 grams in matrass, used raw material contains the large amount of organic impurities titanium tetrachloride, wherein contains TiCl
494.86%, the weight that adds for the first time the aluminum trichloride (anhydrous) compound in raw material is 1.0% of material quantity, carrying out the reflux processing under 136 ± 2 ℃ the temperature after 2.5 hours, add for the second time the aluminum trichloride (anhydrous) compound, the weight of the aluminum chloride that is added for the second time is 0.5% of material quantity, under 136 ℃ ± 2 ℃ temperature, carry out second time reflux again after 1 hour, under 137 ℃ ± 5 ℃ temperature, carry out simple distillation, the TiCl that is steaming
4The middle distilled water that adds, the weight of the distilled water that is added are the first time and 15% of the aluminum trichloride (anhydrous) gross weight that is added the second time, carry out simple distillation again under 137 ℃ ± 5 ℃ temperature, and its result is as follows:
Colourity relative density % TiCl
4Purity %
＜10 99.67 99.63
Embodiment 21
Its working method and used equipment are substantially with embodiment 20, only different is adds aluminum trichloride (anhydrous) for the first time in raw material weight is 1.2% of material quantity, reflux, add for the second time aluminum trichloride (anhydrous), the weight of the aluminum chloride that is added for the second time is 0.3% of material quantity, for the second time reflux, carry out simple distillation, add distilled water, carry out simple distillation, its result is as follows:
Colourity relative density % TiCl
4Purity %
＜10 99.91 99.90
Embodiment 22
Its working method and used equipment are substantially with embodiment 20, only different is, the weight that adds for the first time aluminum trichloride (anhydrous) in raw material is 1.6% of material quantity, and reflux adds aluminum trichloride (anhydrous) for the second time, the weight of the aluminum chloride that is added for the second time is 0.3% of material quantity, reflux is carried out simple distillation for the second time, adds distilled water, carry out simple distillation, its result is as follows: colourity relative density % TiCl
4Purity %＜10 99.91 99.83
Claims (16)
1. a method of removing large amount of organic impurities from titanium tetrachloride is characterized in that, is containing the TiCl of large amount of organic impurities
4Raw material in for the first time add anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of compound wherein, carry out reflux and handle, after the processing, carry out simple distillation or rectifying.
2. according to a kind of method of from titanium tetrachloride, removing large amount of organic impurities of claim 1, it is characterized in that used raw material contains the TiCl that contains 75-98% weight in the titanium tetrachloride of large amount of organic impurities
4
3. according to a kind of method of from titanium tetrachloride, removing large amount of organic impurities of claim 2, it is characterized in that, contain the TiCl of 84-95% weight
4
4. according to a kind of method of from titanium tetrachloride, removing large amount of organic impurities of claim 1, it is characterized in that, the weight that adds for the first time anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of compound wherein be contain large amount of organic impurities the titanium tetrachloride material quantity 0.1～6%.
5. according to a kind of method of from titanium tetrachloride, removing large amount of organic impurities of claim 4, it is characterized in that, the weight that adds for the first time anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of compound wherein be contain large amount of organic impurities the titanium tetrachloride material quantity 0.1～2.0%.
6. according to a kind of method of removing large amount of organic impurities from titanium tetrachloride of claim 1, it is characterized in that the temperature that reflux is handled is 70～150 ℃, the time that reflux is handled is 0.1～6 hour.
7. according to a kind of method of removing large amount of organic impurities from titanium tetrachloride of claim 6, it is characterized in that the temperature that reflux is handled is 100-150 ℃, the time of reflux is 1～4 hour.
8. according to a kind of method of from titanium tetrachloride, removing large amount of organic impurities of claim 1, it is characterized in that, under 130-155 ℃ temperature, carry out simple distillation.
9. a kind of method of removing large amount of organic impurities from titanium tetrachloride according to Claim 8 is characterized in that, carries out simple distillation under 136-148 ℃ temperature.
10. according to a kind of method of from titanium tetrachloride, removing large amount of organic impurities of claim 1, it is characterized in that, add for the first time anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of compound wherein in process, reflux, the product that carries out simple distillation or rectifying is a raw material, in raw material, add entry, the water yield that is added is carried out simple distillation or rectifying for 1～20% of the anhydrous silicon tetrachloride that adds for the first time, FERRIC CHLORIDE ANHYDROUS, wherein a kind of compound weight of aluminum trichloride (anhydrous).
11. a kind of method of from titanium tetrachloride, removing large amount of organic impurities according to claim 10, it is characterized in that the 10-20% of the anhydrous silicon tetrachloride that the water yield that is added added for the first time, FERRIC CHLORIDE ANHYDROUS, wherein a kind of compound weight of aluminum trichloride (anhydrous).
12. a kind of method of from titanium tetrachloride, removing large amount of organic impurities according to claim 1, it is characterized in that, through adding for the first time wherein a kind of compound of anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous), after reflux is handled, add for the second time anhydrous trichlorosilicane, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of compound wherein, after carrying out the reflux processing second time, carry out simple distillation.
13. a kind of method of removing large amount of organic impurities from titanium tetrachloride according to claim 12 is characterized in that, the temperature of carrying out reflux for the second time is 70-150 ℃, and the time of reflux is 0.1-2 hour.
14. a kind of method of from titanium tetrachloride, removing large amount of organic impurities according to claim 12, it is characterized in that the weight that adds anhydrous silicon tetrachloride, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of compound wherein for the second time is to contain 0.05～1.5% of large amount of organic impurities titanium tetrachloride material quantity.
15. a kind of method of removing large amount of organic impurities from titanium tetrachloride according to claim 13 is characterized in that, the temperature of carrying out reflux for the second time is 100-150 ℃.
16. a kind of method of from titanium tetrachloride, removing large amount of organic impurities according to claim 12, it is characterized in that the water yield that is added is the 10-20% of the first time with the anhydrous silicon tetrachloride that adds for the second time, FERRIC CHLORIDE ANHYDROUS, aluminum trichloride (anhydrous) a kind of anhydrous chloride gross weight wherein.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6790319B2 (en) | 2000-12-01 | 2004-09-14 | Mitsui Chemicals, Inc. | Method for recovering titanium compound, process for preparing titanium halide, and process for preparing catalyst for polymer production |
| CN100425313C (en) * | 2005-05-26 | 2008-10-15 | 贵州省材料技术创新基地 | Technology for separating and enrichment recovering silicon tetrachloride |
| CN101985362A (en) * | 2010-09-29 | 2011-03-16 | 天津大学 | Operation method and device for continuous refining of titanium tetrachloride crude |
| CN102040243B (en) * | 2010-12-25 | 2012-09-12 | 锦州钛业有限公司 | Method for controlling content of silicon tetrachloride in fused salt chlorination process of high titanium slag |
| CN103570080B (en) * | 2013-11-08 | 2015-08-05 | 中南大学 | A kind of method of titanium tetrachloride settling mud synthetical recovery iron trichloride |
| CN104192894A (en) * | 2014-08-14 | 2014-12-10 | 仙桃市中星电子材料有限公司 | Refining method of titanium tetrachloride |
| CN110316755B (en) * | 2019-08-20 | 2022-08-05 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for removing organic matters in titanium tetrachloride |
| CN117303436A (en) * | 2023-10-12 | 2023-12-29 | 攀钢集团攀枝花钢铁研究院有限公司 | A method for removing organic impurities in refined titanium tetrachloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0343901A2 (en) * | 1988-05-23 | 1989-11-29 | Amoco Corporation | Method and apparatus for recovering high purity toluene, hexane titanium tetrachloride and tetrahydrofuran from mixtures |
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1998
- 1998-04-15 CN CN98101540A patent/CN1085677C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0343901A2 (en) * | 1988-05-23 | 1989-11-29 | Amoco Corporation | Method and apparatus for recovering high purity toluene, hexane titanium tetrachloride and tetrahydrofuran from mixtures |
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