CN112707437A - Treatment method of titanium tetrachloride-containing waste liquid - Google Patents
Treatment method of titanium tetrachloride-containing waste liquid Download PDFInfo
- Publication number
- CN112707437A CN112707437A CN201911017918.6A CN201911017918A CN112707437A CN 112707437 A CN112707437 A CN 112707437A CN 201911017918 A CN201911017918 A CN 201911017918A CN 112707437 A CN112707437 A CN 112707437A
- Authority
- CN
- China
- Prior art keywords
- titanium tetrachloride
- titanium
- waste liquid
- distillation
- containing waste
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of industrial waste liquid treatment, and relates to a method for treating 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 in a distillation device, wherein a material containing titanium tetrachloride is separated from the top of the distillation device, and a distillation residual liquid is obtained at the bottom of the distillation device; (3) washing the distillation residual liquid obtained in the step (2) with water to obtain recoverable aromatic hydrocarbon and a titanium-containing water phase; (4) and (4) drying the titanium-containing water phase obtained in the step (3) to obtain hydrochloric acid and titanium-rich solid powder. The invention provides a simple and practical method, the high boiling point solvent used does not have adverse effect on the preparation of the catalyst, so that the integral distillation operation is easier to be implementedAnd the operation cost is reduced.
Description
Technical Field
The invention belongs to the field of industrial waste liquid treatment, and particularly relates to a method for treating titanium tetrachloride-containing waste liquid.
Background
In the industrial production of polyolefin, titanium catalysts are widely used because of their high catalytic efficiency and low price. One common method of preparing such catalysts is to first prepare a magnesium solution, for example by reacting a magnesium or magnesium compound with a relevant solvent in the presence of a hydrocarbon promoter, and then prepare a magnesium supported catalyst by reacting the magnesium solution with a halogen containing compound, such as titanium tetrachloride, 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 the crude solvent from the top of the tower, obtaining the titanium tetrachloride and the high-boiling residues from the bottom of the tower, separating the titanium tetrachloride and the high-boiling residues through a hydrocarbon solvent rectifying tower and a titanium tetrachloride rectifying tower respectively to obtain the required hydrocarbon solvent and titanium tetrachloride product, feeding the materials in the bottoms of the hydrocarbon solvent rectifying tower and the titanium tetrachloride rectifying tower into a dry distillation kettle for further distillation, discharging residual liquid containing the titanium tetrachloride and the high-boiling residues from the dry distillation kettle, dehydrating and washing the residual liquid with water to hydrolyze and neutralizing with alkali, and then discharging the residual liquid as waste water. Under the condition of higher titanium tetrachloride recovery rate, the content of high-boiling-point substances in the tower kettle material is higher, and when the content of the high-boiling-point substances is higher, the viscosity of the material is higher, the fluidity is poor, and the coking of the kettle wall can be caused by longer retention time in a high-temperature state. The process has the following problems: in order to avoid the shutdown caused by tower blockage and coking of the kettle wall, the fluidity of the materials is 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, and the treatment capacity of three wastes is increased; a large amount of acid water containing various organic matters is generated in the hydrolysis process, then neutralization treatment is carried out by alkali, and finally a large amount of waste water and waste residues are generated and need further treatment, so that increasingly serious environmental protection and economic pressure are met.
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.
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 contains unreacted titanium tetrachloride, alkoxy titanium and an electron donor, and the method 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 difficult to dissolve in water; the boiling point of the organic solvent is 180-200 ℃: the boiling point of the organic solvent is higher than that of the titanium tetrachloride and lower than that of the alkoxy titanium; (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 organic solvent used has a boiling point of 180 ℃ to 200 ℃, and specifically to the examples, all phenols are used, which totals 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 toxic substances, and more importantly, for polyolefin catalysts, which belong to harmful substances, and are catalyst poisons, the introduction of the above-mentioned phenolic substances in the recovery distillation system represents a potentially significant risk for the relevant catalyst preparation. Therefore, this method solves some problems to some extent, but does not have practical application value in view of the overall process.
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 art for 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 if the white oil is mixed into a catalyst preparation raw material system, the dissolution effect of the magnesium compound is seriously influenced, and the dissolution is an important step in the preparation of the dissolution-precipitation type titanium magnesium catalyst, so that the method also has obvious application limitation for the preparation of the related catalyst.
CN201110303198.7 discloses a treatment method for titanium-containing waste liquid produced by polyolefin catalyst, which comprises the following process steps: (1) mixing titanium-containing waste liquid with water according to the weight ratio of 1: 0.5-1: 3wt, and carrying out hydrolysis treatment to obtain a hydrolysate: mixing lime powder (Ca (OH)2) Adding the hydrolysate in the step (1) into a reactor, and (2) transferring the hydrolysate in the step (1) into the reactor to react with lime (Ca (OH)2) The powder is subjected to neutralization reaction, controlling Ca (OH)2Ratio of powder to original titanium-containing waste liquid such that Ca (OH)2The powder reacts with the hydrolysate to form solid residues. The invention adopts solid lime Ca (OH)2The powder is used as an alkali neutralizer, and the final treatment product is solid waste residue.
CN201110303200.0 discloses a method for recycling titanium-containing waste liquid, which comprises the following process steps: slaked lime (Ca (OH)2) And the lime milk and water are prepared into lime milk in a lime milk storage tank according to a certain proportion: placing the prepared certain amount of lime milk in a reactor: directly adding a certain amount of titanium-containing waste liquid into the reactor, controlling the adding speed of the titanium-containing waste liquid to ensure that the reaction temperature does not exceed 90 ℃, and finally reacting to form solid waste residue TiO2/CaCl2·nH2O。
Although the method reduces the generation of acid water to a certain extent, the obtained solid waste residue still contains a small amount of water and a large amount of organic matters, and the subsequent treatment still needs to be further carried out by adopting the current general method, so that the treatment process is complex.
Disclosure of Invention
Aiming at the prior art, the inventor of the invention breaks through the thought limitation of the prior art, and provides a simpler, more convenient and more practical method based on a brand-new thought, and the used high-boiling point solvent can not generate adverse effect on the preparation of the catalyst, so that the whole distillation operation is easier to implement, and the related operation cost is reduced.
In order to achieve the above object, the present invention provides a method for treating a titanium tetrachloride-containing waste liquid, which is a titanium tetrachloride-containing waste liquid produced in a process for producing a titanium-based polyolefin catalyst, 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-6，20≥n≥7；
(2) Distilling the mixture obtained in the step (1) in a distillation device, wherein a material containing titanium tetrachloride is separated from the top of the distillation device, and a distillation residual liquid is obtained at the bottom of the distillation device;
(3) washing the distillation residual liquid obtained in the step (2) with water to obtain recoverable aromatic hydrocarbon and a titanium-containing water phase;
(4) and (4) drying the titanium-containing water phase obtained in the step (3) to obtain hydrochloric acid and titanium-rich solid powder.
Compared with the prior art, the method avoids the scaling and blocking tendencies in the distillation process of the prior method, and the used high-boiling point solvent can not generate adverse effect on the preparation of the catalyst, so that the whole distillation operation is easier to implement, and the related operation cost is reduced. In addition, after distillation treatment, the distillation residual liquid hardly contains titanium tetrachloride components, the washed organic waste liquid can be recycled, and can also be directly incinerated, so that the treatment cost is low, and the washed titanium-containing water phase can be dried to obtain titanium-rich solid powder which can be recycled. 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 treating titanium tetrachloride-containing waste liquid, which is titanium tetrachloride-containing waste liquid generated in the preparation process of a polyolefin catalyst, and 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, wherein a material containing titanium tetrachloride is separated from the top of the distillation device, and a distillation residual liquid is obtained at the bottom of the distillation device;
(3) washing the distillation residual liquid obtained in the step (2) with water to obtain recoverable aromatic hydrocarbon and a titanium-containing water phase;
(4) and (4) drying the titanium-containing water phase obtained in the step (3) to obtain hydrochloric acid and titanium-rich solid powder.
The titanium tetrachloride-containing waste liquid produced in the production process of the titanium-based polyolefin catalyst of the present invention includes both the catalyst mother liquid produced in the production process of the titanium-based polyolefin catalyst and the residual liquid containing titanium tetrachloride and high boiling substances obtained by distilling the catalyst mother liquid produced in the production process of the titanium-based polyolefin catalyst to remove a part of titanium tetrachloride (i.e., the titanium tetrachloride-containing distillation residual liquid produced in the recovery process of the titanium-based polyolefin catalyst solvent).
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; 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 step (2) of 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.
According to the method of the invention, in the step (2), the titanium tetrachloride-containing material separated from the top of the distillation apparatus may be titanium tetrachloride or a mixture of titanium tetrachloride and high-boiling aromatic hydrocarbons, and the titanium tetrachloride-containing material may be further subjected to rectification in a rectification column to recover titanium tetrachloride, and the obtained high-boiling aromatic hydrocarbons may be recycled, for example, recycled to the distillation apparatus.
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.
During water washing, the addition amount of water is preferably 0.1-5 times, more preferably 0.2-1 times of the volume of the distillation residual liquid, and excessive water amount is not beneficial to oil-water separation of a hydrolysis phase and subsequent control of drying cost.
And drying the separated water-washed water phase to obtain hydrochloric acid which can be further utilized and titanium-rich solid powder. The drying may be by conventional drying means, preferably by vacuum drying or spray drying.
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 liquid (here, specifically, titanium tetrachloride-containing mother liquid or titanium tetrachloride-containing distillation residue) used in the following examples 1 to 9 and comparative examples 1 to 3 was prepared by the following steps: 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 distillation waste liquid containing titanium tetrachloride (here, specifically, mother liquid containing titanium tetrachloride or distillation residue containing titanium tetrachloride) used in the following examples 10 to 18 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, continuing to maintain 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 container, carrying out conventional normal pressure distillation treatment at 110-185 ℃, 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 about 500ml, stopping distillation, adding 50ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.5%.
Example 2
500ml of distillation residual liquid containing titanium tetrachloride 500ml and 500ml of diethylbenzene are evenly mixed in a container, conventional reduced pressure distillation treatment is carried out at 80-125 ℃ and 40-10 kPa, a material containing titanium tetrachloride is separated out at the top of a distillation device, and a material with a high boiling point is obtained at the bottom. When the residual material in the system is about 500ml, stopping distillation, adding 50ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 97.8%.
Example 3
Mixing 1000ml of mother liquor containing titanium tetrachloride and 500ml of 1,2, 4-trimethylbenzene in a container uniformly, carrying out conventional normal pressure distillation treatment at 110-185 ℃, 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 about 500ml, stopping distillation, adding 100ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.2%.
Example 4
And (2) uniformly mixing 1000ml of distillation residual liquid containing titanium tetrachloride and 500ml of 1,2, 4-trimethylbenzene 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 about 500ml, stopping distillation, adding 100ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.5%.
Example 5
Mixing 1000ml of mother liquor containing titanium tetrachloride and 200ml of 1,2, 3-trimethylbenzene in a container 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 a distillation device, and obtaining a material with a high boiling point at the bottom. When the residual materials in the system are about 200ml, stopping distillation, adding 200ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 97.8%.
Example 6:
and (2) uniformly mixing 1000ml of distillation residual liquid containing titanium tetrachloride and 200ml of 1,2, 3-trimethylbenzene in a container, carrying out conventional normal pressure distillation treatment at 110-185 ℃, 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 materials in the system are about 200ml, stopping distillation, adding 200ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.6%.
Example 7
Mixing 1000ml of mother liquor containing titanium tetrachloride and 300ml of 1,3, 5-trimethylbenzene in a container 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 a distillation device, and obtaining a material with a high boiling point at the bottom. When the residual material in the system is about 300ml, stopping distillation, adding 300ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.7%.
Example 8
And (2) uniformly mixing 1000ml of distillation residual liquid containing titanium tetrachloride and 300ml of 1,3, 5-trimethylbenzene 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 about 300ml, stopping distillation, adding 300ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.0%.
Example 9
Uniformly mixing 500ml of titanium tetrachloride-containing mother liquor and 1000ml of propyl benzene in a container, carrying out conventional reduced pressure distillation treatment at 80-125 ℃ under 40-10 kPa, separating titanium tetrachloride-containing materials at the top of a distillation device, and obtaining high-boiling-point materials at the bottom. When the residual material in the system is about 1000ml, stopping distillation, adding 100ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.8%.
Example 10
Uniformly mixing 500ml of distillation residual liquid containing titanium tetrachloride and 1000ml of propyl benzene 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 about 1000ml, stopping distillation, adding 100ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.7%.
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 materials in the system are about 2000ml, stopping distillation, adding 100ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.5%.
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 materials in the system are about 2000ml, stopping distillation, adding 100ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.7%.
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 about 1500ml, stopping distillation, adding 150ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.2%.
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 about 600ml, stopping distillation, adding 150ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 98.6%.
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 about 300ml, stopping distillation, adding 600ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery of titanium tetrachloride in this process was 97.6%.
Example 16
Uniformly mixing 500ml of distillation residual liquid containing titanium tetrachloride (25 g of ethoxy titanium is measured) with 500ml of diethylbenzene and 15 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 about 500ml, stopping distillation, adding 500ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery rate of titanium tetrachloride in the method is more than 99 percent.
Example 17
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 about 500ml, stopping distillation, adding 300ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery rate of titanium tetrachloride in the method is more than 99 percent.
Example 18
Uniformly mixing 500ml of distillation residual liquid containing titanium tetrachloride (25 g of ethoxy titanium is measured) with 500ml of diethylbenzene and 25 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 materials in the system are less than 500ml, stopping distillation, adding 100ml of water for full reaction, standing for separation, washing the oil phase with water, and drying for recycling; spray drying the water phase to obtain corresponding hydrochloric acid and titanium-rich solid powder. The recovery rate of titanium tetrachloride in the method is more than 99 percent.
Comparative example 1
And (3) carrying out conventional normal pressure distillation treatment on 500ml of mother liquor containing titanium tetrachloride at the temperature of 80-150 ℃, stopping distillation when the system is obviously viscous, and obtaining a residual material of about 125ml 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, stopping distillation when the system is obviously viscous, wherein the residual material is about 120ml and contains a large amount of titanium tetrachloride. 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 treating titanium tetrachloride-containing waste liquid generated in the preparation process of a titanium polyolefin catalyst is characterized by comprising 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-620. gtoreq.n.gtoreq.7, preferably 20. gtoreq.n.gtoreq.8;
(2) distilling the mixture obtained in the step (1) in a distillation device, wherein a material containing titanium tetrachloride is separated from the top of the distillation device, and a distillation residual liquid is obtained at the bottom of the distillation device;
(3) washing the distillation residual liquid obtained in the step (2) with water to obtain recoverable aromatic hydrocarbon and a titanium-containing water phase;
(4) and (4) drying the titanium-containing water phase obtained in the step (3) to obtain hydrochloric acid and titanium-rich solid powder.
2. The method for treating a titanium tetrachloride-containing waste liquid as defined 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; preferably, the aromatic hydrocarbon is selected from at least one of propylbenzene, isopropylbenzene, 1,2, 4-trimethylbenzene, 1,2, 3-trimethylbenzene, 1,3, 5-trimethylbenzene, p-methylisopropylbenzene, sec-butylbenzene, tert-butylbenzene, isobutylbenzene and methylisobutylbenzene.
3. The method for treating a titanium tetrachloride-containing waste liquid as claimed in claim 1, wherein the aromatic hydrocarbon has a boiling point of 150 to 210 ℃, preferably 150 to 179 ℃.
4. The method for treating 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, preferably, the volume ratio of the aromatic hydrocarbon to the titanium tetrachloride-containing waste liquid is 0.1-2.0: 1.
5. the method for treating a titanium tetrachloride-containing waste liquid as claimed in claim 1, wherein the titanium tetrachloride-containing waste liquid contains titanium tetrachloride, an organic solvent, an alkoxy titanium, a halogenated alkoxy titanium; adding anhydrous aluminum chloride into the mixture, wherein the weight ratio of the added amount of the anhydrous aluminum chloride to alkoxy titanium in the titanium tetrachloride-containing waste liquid is 0.2-3.0: 1.
6. the method for treating a titanium tetrachloride-containing waste liquid as claimed in claim 1, wherein the weight ratio of the amount of the anhydrous aluminum chloride to the amount of the alkoxy titanium in the titanium tetrachloride-containing waste liquid is from 0.6 to 1.0: 1.
7. the method for treating a titanium tetrachloride-containing waste liquid as claimed in claim 1, wherein the titanium tetrachloride-containing material is subjected to rectification in a rectifying tower to recover titanium tetrachloride.
8. The method for treating a titanium tetrachloride-containing waste liquid as claimed in claim 1, wherein the amount of water added in the step (3) is 0.1 to 5 times the volume of the distillation residue; preferably 0.2 to 1 times.
9. The method for treating a titanium tetrachloride-containing waste liquid as described in claim 1, wherein in the step (4), the drying is vacuum drying or spray drying.
10. The method for treating a titanium tetrachloride-containing waste liquid as claimed in any one of claims 1 to 9, wherein the titanium-containing waste liquid is a catalyst mother liquid produced in a production process of a titanium-based polyolefin catalyst, or a residual liquid containing titanium tetrachloride and a high boiling substance obtained by distilling a part of titanium tetrachloride from a catalyst mother liquid produced in a production process of a titanium-based polyolefin catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911017918.6A CN112707437A (en) | 2019-10-24 | 2019-10-24 | Treatment method of titanium tetrachloride-containing waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911017918.6A CN112707437A (en) | 2019-10-24 | 2019-10-24 | Treatment method of titanium tetrachloride-containing waste liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112707437A true CN112707437A (en) | 2021-04-27 |
Family
ID=75541500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911017918.6A Pending CN112707437A (en) | 2019-10-24 | 2019-10-24 | Treatment method of titanium tetrachloride-containing waste liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112707437A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115282627A (en) * | 2022-07-05 | 2022-11-04 | 中国科学院过程工程研究所 | Purification device and purification method of 1, 5-pentanedicarbamic acid ester |
| CN116041981A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for treating polyolefin catalyst tower bottom liquid extraction precipitate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5242549A (en) * | 1991-12-06 | 1993-09-07 | Shell Oil Company | Distillation separation process of titanium tetrachloride and halohydrocarbon |
| CN103420437A (en) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | Recovery processing method of titanium-containing waste liquid |
| CN106277046A (en) * | 2015-06-24 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of processing method containing titanium tetrachloride waste liquid |
-
2019
- 2019-10-24 CN CN201911017918.6A patent/CN112707437A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5242549A (en) * | 1991-12-06 | 1993-09-07 | Shell Oil Company | Distillation separation process of titanium tetrachloride and halohydrocarbon |
| CN103420437A (en) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | Recovery processing method of titanium-containing waste liquid |
| CN106277046A (en) * | 2015-06-24 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of processing method containing titanium tetrachloride waste liquid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041981A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for treating polyolefin catalyst tower bottom liquid extraction precipitate |
| CN115282627A (en) * | 2022-07-05 | 2022-11-04 | 中国科学院过程工程研究所 | Purification device and purification method of 1, 5-pentanedicarbamic acid ester |
| CN115282627B (en) * | 2022-07-05 | 2024-03-01 | 中国科学院过程工程研究所 | Purification device and purification method of 1, 5-pentanediamine carbamate |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2018023491A1 (en) | Method for recovering titanium (halo) alkoxide from a waste liquid | |
| KR20200034750A (en) | Method for producing polyether ketone ketone | |
| CN112707437A (en) | Treatment method of titanium tetrachloride-containing waste liquid | |
| CZ2018120A3 (en) | A method of producing terephthalic acid from waste polyethylene terephthalate | |
| CN103420437A (en) | Recovery processing method of titanium-containing waste liquid | |
| CN1639067B (en) | Treatment of a titanium tetrachloride-containing waste stream | |
| CN112707435A (en) | Method for recovering refined titanium tetrachloride from titanium tetrachloride-containing waste liquid | |
| CN102336432A (en) | Separation method for recovering olefin polymerization catalyst mother liquid | |
| MX2013015205A (en) | Method for the isolation of olefin oligomerization products and the decomposition of oligomerization catalyst residues. | |
| CN103420413A (en) | Method of recycling refined titanium tetrachloride from titanium-containing waste liquid | |
| CN112707560B (en) | Treatment method of titanium-containing waste liquid, titanium dioxide raw material and application | |
| CN112707436B (en) | Treatment method of titanium tetrachloride-containing waste liquid | |
| CN112707557B (en) | Treatment method of titanium-containing waste liquid | |
| CN112707561B (en) | Treatment method of titanium-containing waste liquid | |
| CN112707556A (en) | Titanium-containing waste liquid treatment method and titanium-containing dry powder | |
| CN104877167A (en) | Method for recycling additive lithium chloride in polyphenylene sulfide resin production process | |
| CN114426306B (en) | Titanium polyolefin catalyst mother liquor treatment device and method | |
| CN112707449B (en) | Method for treating titanium-containing waste liquid | |
| CN112239224A (en) | Method for recovering titanium tetrachloride | |
| CN112300209B (en) | Method for treating waste liquid generated in production of polyolefin catalyst, obtained titanium tetraalkoxide and application thereof | |
| US5075088A (en) | Production of red phosphorus | |
| CN112707532B (en) | Treatment method of titanium-containing distillation residual liquid, titanium white raw material and application | |
| CN112707530B (en) | Treatment method of titanium-containing distillation residual liquid | |
| CN112707559B (en) | Treatment method of titanium-containing distillation raffinate | |
| CN114426362A (en) | Titanium polyolefin catalyst mother liquor treatment device and method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |