CN112707435A - Method for recovering refined titanium tetrachloride from titanium tetrachloride-containing waste liquid - Google Patents
Method for recovering refined titanium tetrachloride from titanium tetrachloride-containing waste liquid Download PDFInfo
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- CN112707435A CN112707435A CN201911014886.4A CN201911014886A CN112707435A CN 112707435 A CN112707435 A CN 112707435A CN 201911014886 A CN201911014886 A CN 201911014886A CN 112707435 A CN112707435 A CN 112707435A
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- titanium tetrachloride
- waste liquid
- distillation
- containing waste
- titanium
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- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 title claims abstract description 212
- 239000007788 liquid Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000002699 waste material Substances 0.000 title claims abstract description 49
- 238000004821 distillation Methods 0.000 claims abstract description 163
- 239000000463 material Substances 0.000 claims abstract description 126
- 238000009835 boiling Methods 0.000 claims abstract description 49
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims description 38
- 239000010936 titanium Substances 0.000 claims description 38
- 229910052719 titanium Inorganic materials 0.000 claims description 38
- 238000011084 recovery Methods 0.000 claims description 31
- -1 alkoxy titanium Chemical compound 0.000 claims description 25
- GWHJZXXIDMPWGX-UHFFFAOYSA-N 1,2,4-trimethylbenzene Chemical compound CC1=CC=C(C)C(C)=C1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 claims description 20
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 16
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 16
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- BFIMMTCNYPIMRN-UHFFFAOYSA-N 1,2,3,5-tetramethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1 BFIMMTCNYPIMRN-UHFFFAOYSA-N 0.000 claims description 12
- YTZKOQUCBOVLHL-UHFFFAOYSA-N p-methylisopropylbenzene Natural products CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 claims description 8
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 claims description 8
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 claims description 8
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 8
- AFZZYIJIWUTJFO-UHFFFAOYSA-N 1,3-diethylbenzene Chemical compound CCC1=CC=CC(CC)=C1 AFZZYIJIWUTJFO-UHFFFAOYSA-N 0.000 claims description 4
- DSNHSQKRULAAEI-UHFFFAOYSA-N 1,4-Diethylbenzene Chemical compound CCC1=CC=C(CC)C=C1 DSNHSQKRULAAEI-UHFFFAOYSA-N 0.000 claims description 4
- XNMPJDZAHSMAMN-UHFFFAOYSA-N 1-methyl-2-(2-methylpropyl)benzene Chemical compound CC(C)CC1=CC=CC=C1C XNMPJDZAHSMAMN-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 4
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 claims description 4
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 claims description 4
- QHTJSSMHBLGUHV-UHFFFAOYSA-N 2-methylbutan-2-ylbenzene Chemical compound CCC(C)(C)C1=CC=CC=C1 QHTJSSMHBLGUHV-UHFFFAOYSA-N 0.000 claims description 2
- 229940078552 o-xylene Drugs 0.000 claims description 2
- 239000002440 industrial waste Substances 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000012452 mother liquor Substances 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 19
- 238000002156 mixing Methods 0.000 description 18
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- SXSVTGQIXJXKJR-UHFFFAOYSA-N [Mg].[Ti] Chemical compound [Mg].[Ti] SXSVTGQIXJXKJR-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 235000011147 magnesium chloride Nutrition 0.000 description 2
- 150000002681 magnesium compounds Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- ZBZXIGONWYKEMZ-UHFFFAOYSA-N CCO[Ti] Chemical compound CCO[Ti] ZBZXIGONWYKEMZ-UHFFFAOYSA-N 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/02—Halides of titanium
- C01G23/022—Titanium tetrachloride
- C01G23/024—Purification of tetrachloride
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention belongs to the field of industrial waste liquid treatment, and relates to a method for recovering refined titanium tetrachloride from titanium tetrachloride-containing waste liquid. The method comprises the following steps: (1) contacting the titanium tetrachloride-containing waste liquid with at least one aromatic hydrocarbon to obtain a mixture, wherein the aromatic hydrocarbon has a general formula CnH2n‑6N is more than or equal to 20 and more than or equal to 7; (2) distilling the mixture obtained in the step (1) in a distillation device, separating a material containing titanium tetrachloride from the top of the distillation device, and obtaining a material with a high boiling point from the bottom of the distillation device; (3) and (3) feeding the material containing titanium tetrachloride obtained in the step (2) into a rectifying tower for rectifying and recovering titanium tetrachloride.
Description
Technical Field
The invention belongs to the field of industrial waste liquid treatment, and particularly relates to a method for recovering refined titanium tetrachloride from titanium tetrachloride-containing waste liquid.
Background
In the industrial production of polyolefin, titanium catalysts are widely used due to high catalytic efficiency and low price. One common method of preparing such catalysts is currently: the preparation of the magnesium solution is first carried out, for example, by preparing a magnesium solution by reacting magnesium or a magnesium compound with a relevant solvent in the presence of a hydrocarbon assistant, and then reacting the magnesium solution with a halogen-containing compound such as titanium tetrachloride to prepare a magnesium-supported catalyst, during which various promoters may be added for modification. In the above catalyst preparation process, it is usually necessary to wash the obtained solid catalyst component with a hydrocarbon solvent to remove titanium tetrachloride not carried therein, and a catalyst slurry is discharged from the reactor, while producing a catalyst mother liquor containing a liquid-phase material such as a hydrocarbon solvent, titanium tetrachloride and high boiling substances.
The recycling process of the polyolefin catalyst mother liquor which is industrialized at home at present is approximately as follows: the method comprises the steps of firstly feeding a mother liquor mixture containing a hydrocarbon solvent, titanium tetrachloride and high-boiling residues into a mother liquor rough separation tower for distillation, obtaining a crude solvent at the tower top, obtaining titanium tetrachloride and high-boiling residues at the tower bottom, then separating the crude solvent and the high-boiling residues through a hydrocarbon solvent rectifying tower and a titanium tetrachloride rectifying tower respectively to obtain a required hydrocarbon solvent and titanium tetrachloride product, feeding materials in the bottoms of the hydrocarbon solvent rectifying tower and the titanium tetrachloride rectifying tower into a dry distillation kettle for further distillation, and discharging residual liquid containing the titanium tetrachloride and the high-boiling residues discharged from the dry distillation kettle as waste water and waste residues after hydrolysis and alkali neutralization in a water washing kettle. One problem with this process is that: under the condition that the recovery rate of titanium tetrachloride is high, the content of high-boiling substances in the material in the tower kettle is high, the viscosity of the material is high, the fluidity of the material is poor, and the material stays for a long time at a high temperature to cause the coking of the kettle wall, so that the device is stopped. In order to avoid the shutdown caused by tower blockage and coking of the kettle wall, the material fluidity needs to be ensured by reducing the recovery rate of titanium tetrachloride, so that the content of titanium tetrachloride in residual liquid discharged from the bottom of the mother liquor dry distillation kettle is higher, the waste of raw materials is caused, the three-waste treatment capacity is increased, and particularly, a large amount of acid-containing wastewater is easily generated.
At present, few reports are provided on the aspect of post-treatment of catalyst mother liquor, and the reported technologies comprise that a wiped film evaporator is adopted to improve the distillation efficiency, a freezing precipitation is adopted for separation, and a high-boiling point solvent is added to improve the recovery rate of titanium tetrachloride, but the disclosed technologies have various defects in specific application. If a wiped film evaporator is adopted and a freezing precipitation method is adopted, related equipment needs to be added on the basis of the prior art, on one hand, the treatment cost is increased, and on the other hand, the deep distillation of the high-boiling residue still has the risk of agglomeration and solidification in the equipment.
In addition to the above methods, there is a method of increasing the recovery rate of titanium tetrachloride by adding a high boiling point solvent.
(i) CN201210154391.3 discloses a method for recovering and treating a titanium-containing waste liquid, wherein the titanium-containing waste liquid is a residual liquid at the bottom of a distillation tower after a titanium-containing mother liquid is treated by the distillation tower, and the residual liquid contains unreacted titanium tetrachloride, alkoxy titanium and an electron donor, and comprises the following steps: (1) adding a single type of organic solvent into the titanium-containing waste liquid, and fully mixing the organic solvent with the titanium-containing waste liquid: the organic solvent can be well mixed with the titanium-containing waste liquid, the liquidity of the mixed liquid is good, and the organic solvent is insoluble in water: the boiling point of the organic solvent is 180-200 ℃: the boiling point of the organic solvent is higher than that of titanium tetrachloride and lower than that of titanium alkoxide: (2) distilling the obtained mixed solution in a distillation device, and separating titanium tetrachloride from the top of the distillation device: controlling the pressure of a distillation device to be normal pressure, controlling the distillation temperature to be 137-160 ℃, and controlling the distillation time to be 30-90 min; (3) adding alkali solution into the residual mixed solution in the distillation device for hydrolysis treatment, and then recovering the organic solvent.
Although the method mentions the use of a single type of organic solvent, the boiling point of the organic solvent used is 180 ℃ to 200 ℃, and all of the examples use phenols, for a total of 8 examples, 7 of which use phenol and 1 of which use o-cresol. Although the patent can greatly improve the recovery rate of titanium tetrachloride, the patent has the following defects: firstly the phenolic compounds themselves are poisons and, more importantly, for polyolefin catalysts, they are catalyst poisons, the introduction of such phenolics in the recovery distillation system represents a potentially significant risk for the relevant catalyst preparation.
(ii) CN201210153649.8 discloses a method for recovering refined titanium tetrachloride from titanium-containing waste liquid, which comprises the following steps: (1) adding white oil into the titanium-containing waste liquid, and uniformly mixing; (2) distilling the mixture in a distillation device, and separating a mixture of titanium tetrachloride and white oil from the top of the tower; (3) rectifying the mixture of titanium tetrachloride and white oil in a rectifying device to obtain titanium tetrachloride: wherein the boiling range of the white oil is between 150 and 180 ℃; the rectification temperature is controlled between 137 ℃ and 150 ℃.
Although the method is obviously improved compared with the phenolic compound in CN201210154391.3, and the used white oil is not a poison of the polyolefin catalyst, for a person skilled in the field of actually preparing the polyolefin catalyst, the white oil still has related potential risks for the currently mainstream dissolution-precipitation type titanium magnesium catalyst system (such as Chinese patent CN200510117428.5) taking toluene as an auxiliary agent, because the dissolution effect of the magnesium compound is seriously influenced by the white oil mixed into a catalyst preparation raw material system, and the dissolution is a very critical step in the preparation of the dissolution-precipitation type titanium magnesium catalyst, so the method has obvious application limitation.
Disclosure of Invention
The object of the present invention is to overcome the above-mentioned drawbacks of the prior art and to provide a more simple and practical method. Because the high boiling point solvent used does not have adverse effect on the preparation of the catalyst, the whole distillation operation is easier to implement, and the related operation cost is reduced.
The invention provides a method for recovering refined titanium tetrachloride from titanium tetrachloride-containing waste liquid, wherein the titanium tetrachloride-containing waste liquid contains titanium tetrachloride, an organic solvent and at least one of alkoxy titanium and halogenated alkoxy titanium, and the method comprises the following steps:
(1) contacting the titanium tetrachloride-containing waste liquid with at least one aromatic hydrocarbon to obtain a mixture, wherein the aromatic hydrocarbon has a general formula CnH2n-6，20≥n≥7；
(2) Distilling the mixture obtained in the step (1) in a distillation device, separating a material containing titanium tetrachloride from the top of the distillation device, and obtaining a material with a high boiling point from the bottom of the distillation device;
(3) and (3) feeding the material containing titanium tetrachloride obtained in the step (2) into a rectifying tower for rectifying and recovering titanium tetrachloride.
The method can greatly improve the recovery rate of the titanium tetrachloride while avoiding the scaling and blocking tendency in the distillation process of the prior method, and also avoids the risk of introducing potential harmful substances into a catalyst preparation system by the prior method. In addition, after distillation treatment, the distillation residual liquid hardly contains titanium tetrachloride, the waste liquid is easy to treat, and the treatment cost is low. The method of the present invention can be conveniently applied to existing catalyst production systems.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for recovering refined titanium tetrachloride from titanium tetrachloride-containing waste liquid, wherein the titanium tetrachloride-containing waste liquid contains titanium tetrachloride, an organic solvent and at least one of alkoxy titanium and halogenated alkoxy titanium, and the method comprises the following steps:
(1) contacting the titanium tetrachloride-containing waste liquid with at least one aromatic hydrocarbon to obtain a mixture, wherein the aromatic hydrocarbon has a general formula CnH2n-6N is more than or equal to 20 and more than or equal to 7; preferably, 12. gtoreq.n.gtoreq.8;
(2) distilling the mixture obtained in the step (1) in a distillation device, separating a material containing titanium tetrachloride from the top of the distillation device, and obtaining a material with a high boiling point from the bottom of the distillation device;
(3) and (3) feeding the material containing titanium tetrachloride obtained in the step (2) into a rectifying tower for rectifying and recovering titanium tetrachloride.
According to the present invention, the aromatic hydrocarbon is preferably at least one selected from the group consisting of o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, propylbenzene, isopropylbenzene, 1,2, 4-trimethylbenzene, 1,2, 3-trimethylbenzene, 1,3, 5-trimethylbenzene, p-methylisopropylbenzene, 1,2,3, 5-tetramethylbenzene, butylbenzene, sec-butylbenzene, tert-butylbenzene, isobutylbenzene, methylisobutylbenzene, pentylbenzene, and tert-pentylbenzene; further preferably, the aromatic hydrocarbon is at least one selected from the group consisting of propylbenzene, isopropylbenzene, 1,2, 4-trimethylbenzene, 1,2, 3-trimethylbenzene, 1,3, 5-trimethylbenzene, p-methylisopropylbenzene, sec-butylbenzene, tert-butylbenzene, isobutylbenzene, and methylisobutylbenzene.
For the purpose of separation from titanium tetrachloride, the aromatic hydrocarbon preferably has a boiling point of 150-.
According to the method of the invention, the specific adding amount of the aromatic hydrocarbon is different according to the consistency of the titanium tetrachloride-containing waste liquid, and preferably, the volume ratio of the aromatic hydrocarbon to the titanium tetrachloride-containing waste liquid is 0.05-5.0: 1, further preferably, the volume ratio of the aromatic hydrocarbon to the titanium tetrachloride-containing waste liquid is 0.1 to 2.0: 1.
according to the method of the present invention, when the titanium tetrachloride-containing waste liquid contains titanium tetrachloride, an organic solvent, alkoxy titanium, halogenated alkoxy titanium, the step (1) further comprises adding anhydrous aluminum chloride to the mixture. Since the boiling point of alkoxy titanium and halogenated alkoxy titanium is relatively high, the alkoxy titanium and halogenated alkoxy titanium basically remain in high-boiling residues and cannot be recycled, and anhydrous aluminum chloride is added, so that the alkoxy titanium and the halogenated alkoxy titanium contained in the system can be converted into titanium tetrachloride and distilled and recycled. The weight ratio of the added amount of the anhydrous aluminum chloride to the alkoxy titanium in the titanium tetrachloride-containing waste liquid is 0.2-3.0: 1; preferably 0.6 to 1.0: 1.
in the present invention, the distillation process may be a conventional distillation process, and may be either atmospheric distillation or vacuum distillation, preferably vacuum distillation. The present invention does not require particular distillation conditions, but preferably produces titanium tetrachloride or the corresponding aromatic hydrocarbon by distillation. Generally, the temperature of atmospheric distillation is 110-185 ℃, the temperature of reduced pressure distillation is 80-125 ℃, and the pressure is 40-10 kPa.
The titanium tetrachloride-containing material separated from the top of the distillation apparatus may be titanium tetrachloride or a mixture of titanium tetrachloride and an aromatic hydrocarbon.
The high boiling point materials (high boiling point aromatic hydrocarbon and other high boiling point substances) obtained at the bottom of the distillation device can be returned to the distillation device for circular distillation or can be subjected to water washing treatment. The mixture containing high boiling point substance left in the distillation still is washed by water (alkali or no alkali is added during washing), then the aromatic hydrocarbon is recovered, and the mixture can be continuously circulated to a distillation device for use after dehydration treatment.
According to the invention, the titanium tetrachloride-containing waste liquid can be titanium tetrachloride-containing mother liquid generated in the preparation process of the titanium-based polyolefin catalyst, and can also be titanium tetrachloride-containing distillation residual liquid generated in the recovery process of a titanium-based polyolefin catalyst solvent, namely, residual liquid containing titanium tetrachloride and high-boiling residues obtained after partial titanium tetrachloride is removed from the catalyst mother liquid generated in the preparation process of the titanium-based polyolefin catalyst through distillation.
Although the different methods may differ slightly in the preparation conditions, they do not constitute an impact on the subsequent process steps. The method is suitable for all titanium tetrachloride-containing waste liquid generated in the preparation process of the titanium polyolefin catalyst.
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.
The titanium tetrachloride-containing waste liquids (here, specifically, titanium tetrachloride-containing mother liquor or titanium tetrachloride-containing distillation residue) used in examples 1 to 8 and comparative examples 1 to 3 were prepared as follows.
Preparation of polyethylene catalyst component: 4.0g of magnesium dichloride, 80ml of toluene, 4.0ml of epichlorohydrin, 4.0ml of tributyl phosphate and 6.4ml of ethanol are sequentially added into a reactor which is fully replaced by high-purity nitrogen, the temperature is raised to 70 ℃ under stirring, and when the solid is completely dissolved to form a uniform solution, the reaction is carried out for 1 hour at the temperature of 70 ℃. The temperature was reduced to 30 ℃ and 4.8ml of 2.2M diethylaluminum chloride was added dropwise and the reaction was maintained at 30 ℃ for 1 hour. The system was cooled to-25 ℃ and 40ml of titanium tetrachloride was slowly added dropwise, and the reaction was stirred for 0.5 hour. The treated inert carrier was added and the reaction was stirred for 0.5 hours. Then 3ml of tetraethoxysilane was added and reacted for 1 hour. The temperature was slowly raised to 85 ℃ and the reaction was carried out for 2 hours. Stopping stirring, standing, quickly layering the suspension, pumping out supernatant, washing twice with toluene and four times with hexane, and blowing with high-purity nitrogen to obtain the solid catalyst component with good fluidity and narrow particle size distribution.
In the preparation process of the catalyst, the generated catalyst mother liquor containing liquid phase materials such as the hydrocarbon solvent, the titanium tetrachloride, the high-boiling residue and the like is the titanium tetrachloride-containing mother liquor. And distilling the mother liquor containing titanium tetrachloride to remove partial titanium tetrachloride to obtain the distillation residual liquid containing titanium tetrachloride.
The titanium tetrachloride-containing waste liquid (here, specifically, titanium tetrachloride-containing mother liquid or titanium tetrachloride-containing distillation residue) used in the following examples 9 to 16 was prepared by the following steps:
preparation of the polypropylene catalyst component: adding 4.8g of magnesium chloride, 75ml of toluene, 7.8ml of epichlorohydrin and 8.2ml of tributyl phosphate into a reactor fully replaced by high-purity nitrogen in turn, heating to 50 ℃ under stirring, maintaining for 2.5 hours, adding 1.2g of phthalic anhydride after the solid is completely dissolved, continuously maintaining for 1 hour, cooling the solution to below-25 ℃, dropwise adding 56ml of titanium tetrachloride within 1 hour, slowly heating to 80 ℃, gradually separating out the solid, adding 2.7ml of diisobutyl phthalate, maintaining for 1 hour at 80 ℃, after heat filtration, adding 100ml of toluene, washing twice to obtain a brown yellow solid, adding 60ml of toluene and 40ml of titanium tetrachloride, treating for 2 hours at 90 ℃, removing the filtrate, and repeatedly treating once. 100ml of toluene was added, the temperature was raised to 110 ℃ and washing was repeated three times for 10 minutes each, and 100ml of hexane was added and washing was repeated two times to obtain 6.77g of a solid.
In the preparation process of the catalyst, the generated catalyst mother liquor containing liquid phase materials such as the hydrocarbon solvent, the titanium tetrachloride, the high-boiling residue and the like is the titanium tetrachloride-containing mother liquor. And distilling the mother liquor containing titanium tetrachloride to remove partial titanium tetrachloride to obtain the distillation residual liquid containing titanium tetrachloride.
The above catalyst preparation methods are listed herein for reference only and do not limit the technology of the present invention. The method of the invention is suitable for all titanium tetrachloride-containing residual liquids produced in the preparation process of titanium polyolefin catalysts.
Example 1
Uniformly mixing 500ml of mother liquor containing titanium tetrachloride and 500ml of diethylbenzene in a distillation device, carrying out conventional normal pressure distillation treatment at 110-185 ℃, separating a material containing titanium tetrachloride at the top of the distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 500ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying and recovering the titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.5%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly diethylbenzene, can be directly used for next distillation according to the condition, and can also be washed and recovered for later use.
Example 2
Uniformly mixing 500ml of distillation residual liquid containing titanium tetrachloride and 500ml of diethylbenzene in a distillation device, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of the distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 500ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying and recovering the titanium tetrachloride, the recovery rate of the titanium tetrachloride is 97.8 percent, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly diethylbenzene, can be directly used for next distillation according to the condition, and can also be washed and recovered for later use.
Example 3
And (2) uniformly mixing 1000ml of mother liquor containing titanium tetrachloride and 500ml of 1,2, 4-trimethylbenzene in a distillation device, carrying out conventional normal pressure distillation treatment at 110-185 ℃, separating a material containing titanium tetrachloride at the top of the distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 500ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying and recovering the titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.2%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly 1,2, 4-trimethylbenzene, can be directly used for next distillation according to circumstances, and can also be washed by water (alkali can be added or not added during washing by water) for later use after recovery.
Example 4
And (2) uniformly mixing 1000ml of distillation residual liquid containing titanium tetrachloride and 500ml of 1,2, 4-trimethylbenzene in a distillation device, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of the distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 500ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying and recovering the titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.5%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly 1,2, 4-trimethylbenzene, can be directly used for next distillation according to circumstances, and can also be washed by water (alkali can be added or not added during washing by water) for later use after recovery.
Example 5
Mixing 1000ml of mother liquor containing titanium tetrachloride and 200ml of 1,2, 3-trimethylbenzene in a distillation device uniformly, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of the distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 200ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying to recover the titanium tetrachloride, the recovery rate of the titanium tetrachloride is 97.8 percent, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly 1,2, 3-trimethylbenzene, can be directly used for next distillation according to circumstances, and can also be washed and recycled for later use.
Example 6
And (2) uniformly mixing 1000ml of distillation residual liquid containing titanium tetrachloride and 200ml of 1,2, 3-trimethylbenzene in a distillation device, carrying out conventional normal pressure distillation treatment at 110-185 ℃, separating a material containing titanium tetrachloride from the top of the distillation device, and obtaining a material with a high boiling point from the bottom. When the residual material in the system is less than 200ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying to recover the titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.6%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly 1,2, 3-trimethylbenzene, can be directly used for next distillation according to circumstances, and can also be washed by water (alkali can be added or not added during washing by water) for later use after recovery.
Example 7
Mixing 1000ml of mother liquor containing titanium tetrachloride and 300ml of 1,3, 5-trimethylbenzene in a distillation device uniformly, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of the distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 300ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying to recover the titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.7%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly 1,3, 5-trimethylbenzene, can be directly used for next distillation according to circumstances, and can also be washed and recycled for later use.
Example 8
And (2) uniformly mixing 1000ml of distillation residual liquid containing titanium tetrachloride and 300ml of 1,3, 5-trimethylbenzene in a distillation device, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of the distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 300ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying to recover the titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.0%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly 1,3, 5-trimethylbenzene, can be directly used for next distillation according to circumstances, and can also be washed and recycled for later use.
Example 9
Uniformly mixing 500ml of mother liquor containing titanium tetrachloride and 1000ml of propyl benzene in a distillation device, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of the distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 1000ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying to recover titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.8%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly propyl benzene, can be directly used for next distillation according to the condition, and can also be washed and recovered for later use.
Example 10
Uniformly mixing 500ml of distillation residual liquid containing titanium tetrachloride and 1000ml of propylbenzene in a distillation device, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of the distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 1000ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying to recover titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.7%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly propyl benzene, can be directly used for next distillation according to the condition, and can also be washed and recovered for later use.
Example 11
Uniformly mixing 500ml of mother liquor containing titanium tetrachloride and 2000ml of 1,2,3, 5-tetramethylbenzene in a container, carrying out conventional reduced pressure distillation treatment at 80-135 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of a distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 2000ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying to recover titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.5%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly 1,2,3, 5-tetramethylbenzene, and can be directly used for next distillation or be washed and recycled for later use.
Example 12
Uniformly mixing 500ml of distillation residual liquid containing titanium tetrachloride and 2000ml of 1,2,3, 5-tetramethylbenzene in a container, carrying out conventional reduced pressure distillation treatment at 80-135 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of a distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 2000ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying to recover titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.7%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly 1,2,3, 5-tetramethylbenzene, and can be directly used for next distillation or be washed and recycled for later use.
Example 13
Uniformly mixing 500ml of distillation residual liquid containing titanium tetrachloride and 1500ml of butylbenzene in a container, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of a distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 1500ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying and recovering the titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.2%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly butylbenzene, can be directly used for next distillation according to the condition, and can also be washed and recovered for later use.
Example 14
And (2) uniformly mixing 1000ml of distillation residual liquid containing titanium tetrachloride and 600ml of pentylbenzene in a container, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of a distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 600ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying to recover the titanium tetrachloride, the recovery rate of the titanium tetrachloride is measured to be 98.6%, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly pentylbenzene, can be directly used for next distillation according to the circumstances, and can also be washed and recycled for later use.
Example 15
Mixing 1000ml of mother liquor containing titanium tetrachloride, 100ml of 1,3, 5-trimethylbenzene and 200ml of 1,2, 4-trimethylbenzene uniformly in a container, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of a distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 300ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying to recover the titanium tetrachloride, the recovery rate of the titanium tetrachloride is 97.6 percent, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual materials mainly comprise 1,3, 5-trimethylbenzene and 1,2, 4-trimethylbenzene, and can be directly used for next distillation or recycled for later use after being washed by water according to the circumstances.
Example 16
Uniformly mixing 500ml of distillation residual liquid containing titanium tetrachloride (25 g of ethoxy titanium is measured) with 500ml of diethylbenzene and 20 g of anhydrous aluminum chloride in a container, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of a distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is less than 500ml, the distillation is stopped, the material containing titanium tetrachloride enters a rectifying tower for rectifying and recovering the titanium tetrachloride, the recovery rate of the titanium tetrachloride is more than 99 percent, and the residual material in the distillation device still has obvious fluidity after being cooled. The residual material is mainly diethylbenzene, can be directly used for next distillation according to the condition, and can also be washed and recovered for later use.
Comparative example 1
And (2) carrying out conventional normal pressure distillation treatment on 500ml of mother liquor containing titanium tetrachloride at the temperature of 80-150 ℃, separating a material containing titanium tetrachloride at the top of a distillation device, and obtaining a material with a high boiling point at the bottom. When the system was clearly viscous, the distillation was stopped, at which point about 125ml of material remained, containing a large amount of titanium tetrachloride. The recovery of titanium tetrachloride in this process was 50%.
Comparative example 2
And (3) carrying out conventional reduced pressure distillation treatment on 200ml of distillation residual liquid containing titanium tetrachloride at 80-120 ℃ under 40-10 kPa, separating a material containing titanium tetrachloride at the top of a distillation device, and obtaining a material with a high boiling point at the bottom. When the system was clearly viscous, the distillation was stopped, at which point about 120ml of residual material, containing a large amount of titanium tetrachloride, was obtained. The recovery of titanium tetrachloride in this process was 51%.
Comparative example 3
Adding 60mL of water into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 30mL of the distillation residual liquid obtained in the comparative example 1 under stirring, maintaining the reaction temperature to be lower than 100 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing the HCl, and obtaining an oil, water and solid three-phase mixture after the reaction is finished. Due to the water and HCl, the mixture was acidic and difficult to incinerate. Particularly, under the increasingly strict environmental requirements, the mixture is difficult to be processed in the catalyst production field, and needs to be transported to a remote area, so that the subsequent processing flow is complicated, the cost is high, and the environmental protection is not facilitated.
It can be seen from the comparison of the examples and comparative examples that, compared with the currently employed method, the present invention provides a more convenient and practical method, which avoids the scaling and blocking tendency in the distillation process of the prior method, improves the recovery rate of titanium tetrachloride in the titanium-containing waste liquid, the used high boiling point solvent does not have adverse effect on the preparation of the catalyst, and avoids the risk of introducing potential harmful substances in the catalyst preparation system of the prior method, thereby making the overall distillation operation easier to implement and reducing the related operation cost. After distillation treatment, the distillation residual liquid almost does not contain titanium tetrachloride, the waste liquid is easy to treat, and the treatment cost is low. In addition, the method of the present invention can be conveniently applied to existing catalyst production systems.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (10)
1. A method for recovering refined titanium tetrachloride from a titanium tetrachloride-containing waste liquid containing titanium tetrachloride, an organic solvent, and at least one of alkoxy titanium and halogenated alkoxy titanium, characterized by comprising the steps of:
(1) contacting the titanium tetrachloride-containing waste liquid with at least one aromatic hydrocarbon to obtain a mixture, wherein the aromatic hydrocarbon has a general formula CnH2n-6N is more than or equal to 20 and more than or equal to 7; preferably, 12. gtoreq.n.gtoreq.8;
(2) distilling the mixture obtained in the step (1) in a distillation device, separating a material containing titanium tetrachloride from the top of the distillation device, and obtaining a material with a high boiling point from the bottom of the distillation device;
(3) and (3) feeding the material containing titanium tetrachloride obtained in the step (2) into a rectifying tower for rectifying and recovering titanium tetrachloride.
2. The method for recovering refined titanium tetrachloride from a titanium tetrachloride-containing waste liquid as claimed in claim 1, wherein said aromatic hydrocarbon is at least one member selected from the group consisting of o-xylene, m-xylene, p-xylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, propylbenzene, isopropylbenzene, 1,2, 4-trimethylbenzene, 1,2, 3-trimethylbenzene, 1,3, 5-trimethylbenzene, p-methylisopropylbenzene, 1,2,3, 5-tetramethylbenzene, butylbenzene, sec-butylbenzene, tert-butylbenzene, isobutylbenzene, methylisobutylbenzene, pentylbenzene and tert-pentylbenzene.
3. The method for recovering refined titanium tetrachloride from a titanium tetrachloride-containing waste liquid as claimed in claim 2, wherein said aromatic hydrocarbon is at least one member selected from the group consisting of propylbenzene, isopropylbenzene, 1,2, 4-trimethylbenzene, 1,2, 3-trimethylbenzene, 1,3, 5-trimethylbenzene, p-methylisopropylbenzene, sec-butylbenzene, tert-butylbenzene, isobutylbenzene and methylisobutylbenzene.
4. The method for recovering refined titanium tetrachloride from a titanium tetrachloride-containing waste liquid as claimed in claim 1, wherein the aromatic hydrocarbon has a boiling point of 150-210 ℃, preferably 150-179 ℃.
5. The method for recovering refined titanium tetrachloride from a titanium tetrachloride-containing waste liquid as claimed in claim 1, wherein the volume ratio of the aromatic hydrocarbon to the titanium tetrachloride-containing waste liquid is from 0.05 to 5.0: 1.
6. the method for recovering refined titanium tetrachloride from a titanium tetrachloride-containing waste liquid as claimed in claim 5, wherein the volume ratio of the aromatic hydrocarbon to the titanium tetrachloride-containing waste liquid is from 0.1 to 2.0: 1.
7. the method according to claim 1, wherein when the titanium tetrachloride-containing waste liquid contains titanium tetrachloride, an organic solvent, an alkoxy titanium and a halogenated alkoxy titanium, the step (1) further comprises adding anhydrous aluminum chloride to the mixture in an amount such that the weight ratio of the anhydrous aluminum chloride to the alkoxy titanium in the titanium tetrachloride-containing waste liquid is from 0.2 to 3.0: 1.
8. the method for recovering refined titanium tetrachloride from a titanium tetrachloride-containing waste liquid as claimed in claim 7, wherein the weight ratio of the amount of the anhydrous aluminum chloride added to the amount of the titanium alkoxide in the titanium tetrachloride-containing waste liquid is from 0.6 to 1.0: 1.
9. the process for recovering refined titanium tetrachloride from a titanium tetrachloride-containing waste liquid as claimed in claim 1, wherein the high boiling point material obtained at the bottom of the distillation apparatus is returned to the distillation apparatus or subjected to a washing treatment with water.
10. The process for recovering refined titanium tetrachloride from a titanium tetrachloride-containing waste liquid as claimed in any one of claims 1 to 9, wherein the titanium tetrachloride-containing waste liquid is a titanium tetrachloride-containing mother liquid produced in a production process of a titanium-based polyolefin catalyst or a titanium tetrachloride-containing distillation residue produced in a solvent recovery process of a titanium-based polyolefin catalyst.
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