CN113636590B - Method for purifying nonmetallic impurities in titanium-containing filtrate - Google Patents
Method for purifying nonmetallic impurities in titanium-containing filtrate Download PDFInfo
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- C01G23/024—Purification of tetrachloride
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Abstract
The invention relates to the field of polyolefin catalysts, and discloses a method for purifying nonmetallic impurities in titanium-containing filtrate, which comprises the following steps: 1) Evaporating the titaniferous filtrate through a thin film evaporator to obtain titaniferous distillate; 2) Mixing the titanium-containing distillate with an inert organic solvent to obtain a mixture of the titanium-containing distillate and the inert organic solvent; 3) Standing and settling the mixture, and carrying out solid-liquid separation on settled precipitate and supernatant; 4) And distilling and separating the supernatant to obtain titanium tetrachloride and an organic solvent, wherein the titanium-containing filtrate is one or more than two of mother liquor and titanium treatment liquor generated in the preparation process of the ethylene polymerization catalyst. The method of the invention obviously improves the utilization rate of raw materials, greatly reduces the waste acid sludge generated in the treatment process, effectively removes nonmetallic impurities in the filtrate, and greatly improves the recovery rate of titanium tetrachloride in the titaniferous distillate.
Description
Technical Field
The invention relates to the field of polyolefin catalysts, in particular to a method for purifying nonmetallic impurities in titanium-containing filtrate.
Background
In the industrial production of polyolefin, titanium-based catalysts have been widely used because of high catalytic efficiency and low price. One common method for preparing such catalysts is to first prepare a magnesium-containing solution, for example, by uniformly dispersing magnesium or a magnesium compound in one or more solvents, adding an organic aid to the mixture to prepare a magnesium-containing solution, and then reacting the magnesium-containing solution with a halogen-containing compound such as titanium tetrachloride to prepare a catalyst having a main structure of magnesium or a magnesium compound, wherein various promoters for improving the performance may be added to the catalyst, and the promoters contain phosphorus and silicon. In the above catalyst preparation process, it is generally necessary to wash the obtained solid catalyst primary particles with an organic solvent to remove the titanium tetrachloride not carried therein, and the catalyst dispersion liquid is discharged from the reactor while producing a catalyst titanium-containing filtrate of the organic solvent, titanium tetrachloride, an alkyl compound, and a liquid phase material containing phosphorus, silicon compound, and the like.
The recycling process of the titanium-containing filtrate of the ethylene polymerization catalyst which is industrialized at home at present is approximately as follows: the method comprises the steps of feeding a titanium-containing filtrate mixture containing an organic solvent, titanium tetrachloride, a nonmetallic compound and the like into a filtrate coarse separation tower for rectification, obtaining a coarse solvent from the tower top, separating titanium tetrachloride, an alkyl compound and the like from the tower bottom through an organic solvent rectification tower and a titanium tetrachloride rectification tower respectively to obtain required organic solvent and titanium tetrachloride products, feeding materials in the organic solvent rectification tower and the titanium tetrachloride rectification tower kettle into rectification equipment for further rectification, dehydrating tower bottoms containing titanium tetrachloride, an alkyl compound and phosphorus and a silicon compound discharged from the rectification kettle, hydrolyzing the tower bottoms, and discharging acid residues. One problem with this process is that: the hydrolysis process generates a large amount of waste acid sludge containing various organic matters, and further treatment is required, so that the serious environmental protection and economic pressure are faced.
CN201110303198.7 discloses a method for treating waste liquor containing titanium produced by polyolefin catalyst, which comprises the following steps: (1) Mixing the titanium-containing waste liquid with water according to the weight ratio of 1:0.5-1:3wt%, and performing hydrolysis treatment to obtain a hydrolysate: lime powder (Ca (OH) 2 ) Adding into a reactor, (2) transferring the hydrolysate in the step (1) into the reactor and lime (Ca (OH) 2 ) The powder is subjected to neutralization reaction, ca (OH) is controlled 2 Ratio of powder to original titanium-containing waste liquid, ca (OH) 2 The powder reacts with the hydrolysate to form solid slag. The invention adopts solid lime Ca(OH) 2 The powder is used as an alkali neutralizer, so that the water required by alkali liquor preparation in the conventional method is saved, the final waste treatment capacity is reduced, the waste emission is reduced, the final treatment product is solid waste residues, the solid waste residues can be further treated according to the solid waste, the solid waste residues are convenient to transport relative to the waste liquid, the subsequent treatment mode can adopt conventional means such as incineration, landfill and the like for treatment, and the treatment cost is saved.
CN101065506B discloses a process for recovering titanium tetrachloride from waste liquid, which relates to a process for continuously recovering titanium tetrachloride from waste liquid containing TiCl4 and byproducts, wherein the waste liquid is subjected to an evaporation step in the form of a flowing liquid film with a residence time of less than minutes and a temperature of more than 90 ℃.
CN103221344a discloses a process for recovering transition metal tetrahalides and hydrocarbons from waste streams: (a) Establishing a mixed stream comprising a transition metal tetrahalide and a transition metal alkyl halide; (b) Forming a falling liquid film from the mixed stream of step (a) at a temperature of 25 ℃ to 85 ℃ and an absolute pressure of 0.05 to 0.6 bar; (c) Establishing a first vapor stream comprising 90% to 100% recoverable components and a second liquid stream comprising about 10% to 80% haloalkyltitanium oxide from the membrane of step (b).
In the first method, although the generation of acid water is reduced to a certain extent, the obtained solid waste residue obviously needs subsequent further treatment due to the fact that the solid waste residue contains a large amount of organic matters, and the treatment flow is complex. The second method, while improving titanium tetrachloride recovery, forms oily clumps in the waste liquid at high temperatures, affecting the subsequent evaporation process. In the third method, although conditions such as the temperature of a thin film evaporator are optimized, and the problem of high-temperature coking of materials is solved, impurities in the materials are not effectively removed, and the recovery rate of tetrahalides is not ideal.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide the method for purifying the nonmetallic impurities in the titaniferous filtrate, which can obviously improve the utilization rate of raw materials, greatly reduce the waste acid sludge generated in the treatment process, effectively remove the nonmetallic impurities in the filtrate and greatly improve the recovery rate of titanium tetrachloride in the titaniferous distillate.
In order to achieve the above object, the present invention provides a method for purifying nonmetallic impurities in a titanium-containing filtrate, the method comprising the steps of:
1) Evaporating the titaniferous filtrate through a thin film evaporator, and collecting bottom distillate to obtain titaniferous distillate;
2) Mixing the titanium-containing distillate with an inert organic solvent to obtain a mixture of the titanium-containing distillate and the inert organic solvent, wherein the inert organic solvent is one or more of alkane and cycloalkane;
3) Standing and settling the mixture obtained in the step 2), and carrying out solid-liquid separation on settled precipitate and supernatant;
4) Distilling and separating the supernatant obtained in the step 3) to obtain titanium tetrachloride and an organic solvent respectively,
wherein the titanium-containing filtrate is one or more than two of mother liquor and titanium treatment liquid generated in the preparation process of the ethylene polymerization catalyst.
Preferably, the titanium tetrachloride obtained in step 4) is used for preparing an ethylene polymerization catalyst, and the organic solvent obtained in step 4) is used as the inert organic solvent.
Preferably, the titaniferous filtrate is efficiently evaporated by a thin film evaporator, a flowing liquid film is formed on the inner wall of the evaporator, the thickness of the liquid film is less than 3cm, and the residence time is less than 5 minutes.
Preferably, the titanium-containing filtrate is subjected to reduced pressure distillation through a thin film evaporator, and the conditions of the reduced pressure distillation include: the relative vacuum degree is-50 Kpa to-98 Kpa, and the temperature is 65-110 ℃.
Preferably, the titaniferous filtrate contains toluene and titanium tetrachloride, the titaniferous filtrate is efficiently evaporated by a thin film evaporator, the toluene and part of the titanium tetrachloride form vapor flow to be separated from the top, and the titaniferous distillate containing titanium tetrachloride, phosphorus and silicon compounds is obtained from the bottom.
Preferably, the cycloalkane is one or more of cyclopentane, cyclohexane, dimethylcyclopropane, ethylcyclopropane, methylcyclobutane, and methylcyclopentane.
Preferably, the alkane is one or more of pentane, hexane, heptane and octane.
Preferably, the volume ratio of the inert organic solvent to the titanium-containing distillate is from 0.1 to 10:1, more preferably from 1 to 6:1.
Preferably, the temperature during mixing is between-20 and 50 ℃ and the mixing time is between 0.1 and 10 hours.
Preferably; the temperature is-20 to 30 ℃ and the time is 0.1 to 10 hours after mixing and standing.
Preferably, the inert organic solvent content in the supernatant composition is 70-85 wt% and the titanium tetrachloride content is 15-30 wt%.
Preferably, the titanium tetrachloride and the organic solvent are separated by one or more of atmospheric distillation, vacuum distillation, atmospheric distillation and vacuum distillation.
Preferably, the titanium tetrachloride and the organic solvent are separated by distillation.
Preferably, the temperature of the rectification is 130-138 ℃.
Preferably, the solid-liquid separation is filtration and/or centrifugation.
Compared with the prior art that the tower bottom liquid is obtained after the tower bottom liquid is treated by tower bottom type equipment and then is treated by water to generate a large amount of wastewater containing organic matters and titanium dioxide, the method adopts the thin film evaporator to evaporate, uses inert organic solvent to mix and extract deep recovery titanium-containing distillate, and further rectifies and purifies the supernatant obtained by separation, thereby obtaining qualified titanium tetrachloride and organic solvent raw materials and reducing the consumption of titanium tetrachloride and organic solvent. The precipitate produced by mixing or standing the mixture of the titanium-containing distillate and the organic solvent is reprocessed and dried to form powder, which has certain fluidity and is favorable for packaging, transportation and use. The precipitate contains a large amount of nonmetallic impurities, can be used for common solid waste treatment, and has obvious environmental protection and economic benefits.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The method for purifying nonmetallic impurities in the titaniferous filtrate provided by the invention comprises the following steps:
1) Evaporating the titaniferous filtrate through a thin film evaporator, and collecting bottom distillate to obtain titaniferous distillate;
2) Mixing the titanium-containing distillate with an inert organic solvent to obtain a mixture of the titanium-containing distillate and the inert organic solvent, wherein the inert organic solvent is one or more of alkane and cycloalkane;
3) Standing and settling the mixture obtained in the step 2), and carrying out solid-liquid separation on settled precipitate and supernatant;
4) Distilling and separating the supernatant obtained in the step 3) to obtain titanium tetrachloride and an organic solvent respectively,
wherein the titanium-containing filtrate is one or more than two of mother liquor and titanium treatment liquid generated in the preparation process of the ethylene polymerization catalyst.
According to the present invention, preferably, titanium tetrachloride obtained in step 4) is used for preparing an ethylene polymerization catalyst, and the organic solvent obtained in step 4) is used as the inert organic solvent.
According to the invention, the titanium-containing filtrate is one or a mixture of more than two of mother liquor and titanium treatment liquid generated in the preparation process of the ethylene polymerization catalyst.
In the preparation process of the ethylene polymerization catalyst, primary catalyst particles are formed in the catalyst preparation synthesis stage, the mother liquor is obtained by filtering a liquid phase after standing, and the titanium treatment liquid is obtained by washing the primary catalyst particles with titanium tetrachloride and filtering.
The titanium-containing filtrate contains: 30 to 50 weight percent of toluene and 40 to 70 weight percent of titanium tetrachloride.
According to the invention, in the step 1), the titaniferous filtrate is efficiently evaporated by a thin film evaporator, a flowing liquid film is formed on the inner wall of the evaporator, the thickness of the liquid film is less than 3cm, and the residence time is less than 5 minutes; preferably, the titaniferous filtrate is efficiently evaporated by a thin film evaporator, a flowing liquid film is formed on the inner wall of the evaporator, the thickness of the liquid film is 0.5-1 cm, and the residence time is 1-4 minutes.
As such a thin film evaporator, for example, a thin film evaporator available from De-Mida Process Equipment (Beijing) Co., ltd. (model VKL 70-4) or a thin film evaporator available from Centipeda chemical machinery Co., ltd. (model GXZ-6B) can be used.
According to the invention, when the titanium-containing filtrate is evaporated by the thin film evaporator, toluene and part of titanium tetrachloride form vapor flow to separate from the top, and titanium tetrachloride, phosphorus and silicon compound are obtained from the bottom. Preferably, the titanium-containing distillate mainly contains: 50 to 65% by weight of titanium tetrachloride, 10 to 20% by weight of silicon and phosphorus compounds.
According to the invention, the titaniferous filtrate is subjected to reduced pressure distillation through a thin film evaporator, and the conditions of the reduced pressure distillation comprise: the relative vacuum degree is-50 Kpa to-98 Kpa, and the temperature is 65-110 ℃; preferably, the conditions of the reduced pressure distillation include: the relative vacuum degree is-50 Kpa to-85 Kpa, and the temperature is 75-110 ℃; more preferably, the conditions of the reduced pressure distillation include: the relative vacuum degree is-50 Kpa to-85 Kpa, and the temperature is 90-110 ℃.
According to the invention, in step 2), the inert organic solvent is one or more of paraffin and naphthene.
Preferably, the cycloalkane is one or more of cyclopentane, cyclohexane, dimethylcyclopropane, ethylcyclopropane, methylcyclobutane, and methylcyclopentane.
Preferably, the alkane is one or more of pentane, hexane, heptane and octane.
According to the invention, the inert organic solvent may also be a low titanium organic solvent wash solution derived from the ethylene polymerization catalyst production process, the titanium content of the wash solution being less than 10mg/ml, preferably less than 5mg/ml, in order to further reduce costs.
According to the invention, in step 2), the volume ratio of the inert organic solvent to the titanium-containing distillate is 1-10: 1, preferably 1 to 6:1, more preferably 3 to 5:1. when the titanium-containing distillate is specifically mixed, the titanium-containing distillate can be added into a container, and then an inert organic solvent is added; or adding an inert organic solvent and then adding the titanium-containing distillate; preferably, the vessel is charged with the inert organic solvent and then with the titanium-containing distillate.
Preferably, the temperature at the time of mixing is-20 to 50 ℃, more preferably 5 to 30 ℃; the mixing time is 0.1 to 10 hours, more preferably 0.5 to 5 hours.
According to the invention, the titanium-containing distillate is mixed with an inert organic solvent and then allowed to stand for delamination. Preferably, the temperature at the time of standing is-20 ℃ to 30 ℃, more preferably-10 ℃ to 30 ℃, still more preferably-10 ℃ to 0 ℃; the standing time is 0.1 to 10 hours, more preferably 0.5 to 5 hours, still more preferably 0.5 to 2 hours, still more preferably 0.5 to 1 hour.
According to the present invention, preferably, in step 3), the solid-liquid separation is filtration and/or centrifugation.
According to the present invention, preferably, the inert organic solvent content in the supernatant composition is 70 to 85 wt% and the titanium tetrachloride content is 15 to 30 wt%.
According to the present invention, preferably, in step 4), the supernatant is separated by one or more of atmospheric distillation, vacuum distillation, atmospheric distillation and vacuum distillation to obtain titanium tetrachloride and an organic solvent.
Preferably, titanium tetrachloride and an organic solvent are obtained by fractionation; preferably, the temperature of the rectification is 130-138 ℃.
The present invention will be described in detail by way of examples, but the present invention is not limited to the following examples.
In the following examples, the titanium tetrachloride content was determined using a type 722 ultraviolet-visible spectrophotometer under experimental conditions: under acidic conditions, the titanium particles complex with hydrogen peroxide to form a yellow-brown complex, which gives the aqueous phase a yellow color.
In the invention, the determination of the toluene content is performed by using an Ageilent 6890N-type gas chromatograph.
In the following examples, the thin film evaporator was a thin film evaporator (model VKL 70-4) available from delbrueck process equipment (beijing).
In the following examples, the titanium-containing filtrate was a mixed solution of a mother liquor and a titanium treatment liquid produced during the preparation of an ethylene polymerization catalyst. The mother liquor is a liquid phase obtained by forming primary catalyst particles in a catalyst preparation and synthesis stage, standing the catalyst particles and filtering the catalyst particles, and the titanium treatment liquid is a titanium treatment liquid obtained by washing and filtering the primary catalyst particles by using titanium tetrachloride. The titanium-containing filtrate contains: 43 wt% toluene, 50.6 wt% titanium tetrachloride.
Example 1
1) Firstly, replacing complete equipment of the thin film evaporator by nitrogen, and adding 500ml of titanium-containing filtrate into a metering bottle; opening a vacuum pump to vacuumize, adjusting a vacuum valve, and controlling the relative vacuum degree of the thin film evaporator to be-50 Kpa; introducing hot oil into a jacket of the thin film evaporator and gradually heating to 110 ℃; and (3) opening a feed valve, adding the titaniferous filtrate into a thin film evaporator, keeping the rotating speed of a scraper rotor constant, dispersing the titaniferous filtrate into a thin film (the thickness of the liquid film is 0.5cm, and the residence time is 2 minutes), and collecting distillate at the bottom of the evaporator to obtain titaniferous distillate.
2) 250mL of hexane was added to a 500mL glass reaction vessel with mechanical stirring, reflux condenser and nitrogen protection, 50mL of titanium-containing distillate was gradually added under stirring, and the mixture was stirred and mixed at room temperature for 2 hours, after the stirring was completed, a dark gray mixture was obtained, and a part of precipitate was visible. The mixture of the titanium-containing distillate and the organic solvent is cooled to-10 ℃, the mixture is allowed to stand still and settle for 0.5 hour at the temperature, the settled precipitate and supernatant are subjected to solid-liquid separation by adopting a filter plate filtration mode, the earth gray precipitate (dry weight is 15.3 g) is collected, 294ml of supernatant is further distilled to obtain 268ml of hexane solution containing titanium tetrachloride, the titanium tetrachloride content in the hexane solution containing titanium tetrachloride is 0.6 weight percent, the distillation temperature is controlled to be 130-136 ℃, and the titanium tetrachloride with the purity of more than 98 weight percent is obtained after distillation. The purified titanium tetrachloride can be used for producing a polyolefin catalyst, the hexane can be recycled in the step (1), the purified titanium tetrachloride can also be used for producing a polyolefin catalyst, and the precipitate can be treated as a general solid waste (wherein the titanium content is 22 wt%, the silicon content is 7 wt% and the phosphorus content is 12 wt%).
Example 2
1) Firstly, replacing complete equipment of the thin film evaporator by nitrogen, and adding 500ml of titanium-containing filtrate into a metering bottle; opening a vacuum pump to vacuumize, adjusting a vacuum valve, and controlling the relative vacuum degree of the thin film evaporator to be-70 Kpa; introducing hot oil into a jacket of the thin film evaporator and gradually heating to 100 ℃; and (3) opening a feed valve, adding the titaniferous filtrate into a thin film evaporator, keeping the rotating speed of a scraper rotor constant, dispersing the titaniferous filtrate into a thin film (the thickness of the liquid film is 0.6cm, and the residence time is 3 minutes), and collecting distillate at the bottom of the evaporator to obtain titaniferous distillate.
2) 200mL of hexane was added to a 500mL glass reaction vessel with mechanical stirring, reflux condenser and nitrogen protection, 50mL of a titanium-containing distillate was gradually added dropwise under stirring, and the mixture was stirred and mixed at room temperature for 2 hours, after the stirring was completed, a dark gray mixture was obtained, and a part of precipitate was visible. The mixture of the titanium-containing distillate and the organic solvent is cooled to 0 ℃, the mixture is allowed to stand and settle for 1 hour at the temperature, the settled precipitate and supernatant are subjected to solid-liquid separation, the earth gray precipitate (dry weight 15.6 g) is collected, 246ml of supernatant is further distilled to obtain 220ml of hexane solution containing titanium tetrachloride, the titanium tetrachloride content in the hexane solution containing titanium tetrachloride is 0.78 weight percent, the distillation temperature is controlled to be 130-136 ℃, and the titanium tetrachloride with the purity of more than 98 weight percent is obtained after distillation. The titanium tetrachloride after rectification and purification can be used for producing a polyolefin catalyst, the hexane can be recycled for the step (1) and also can be used for producing the polyolefin catalyst, and the precipitate can be used as a general solid waste treatment (24 weight percent of titanium, 8 weight percent of silicon and 13 weight percent of phosphorus).
Example 3
1) Firstly, replacing complete equipment of the thin film evaporator by nitrogen, and adding 500ml of titanium-containing filtrate into a metering bottle; opening a vacuum pump to vacuumize, adjusting a vacuum valve, and controlling the relative vacuum degree of the thin film evaporator to be-85 Kpa; introducing hot oil into a jacket of the thin film evaporator and gradually heating to 90 ℃; and (3) opening a feed valve, adding the titaniferous filtrate into a thin film evaporator, keeping the rotating speed of a scraper rotor constant, dispersing the titaniferous filtrate into a thin film (the thickness of the liquid film is 0.5cm, and the residence time is 4 minutes), and collecting distillate at the bottom of the evaporator to obtain titaniferous distillate.
2) 50mL of a titanium-containing distillate was added to a 500mL glass reaction vessel with mechanical stirring, reflux condenser and nitrogen protection, 150mL of hexane was gradually added under stirring, and the mixture was stirred and mixed at room temperature for 2 hours, after the completion of the reaction, a dark gray mixture was obtained, and a part of precipitate was visible. The mixture of the titanium-containing distillate and the organic solvent is cooled to-5 ℃, the mixture is allowed to stand and settle for 0.5 hour at the temperature, the settled precipitate and supernatant are subjected to solid-liquid separation, the earthy precipitate (dry weight 16 g) is collected, 194ml of supernatant is further distilled to obtain 169ml of hexane solution containing titanium tetrachloride, the titanium tetrachloride content in the hexane solution containing titanium tetrachloride is 1 weight percent, the distillation temperature is controlled to be 130-136 ℃, and the purity of titanium tetrachloride is more than 98 percent after distillation. The titanium tetrachloride after rectification and purification can be used for producing a polyolefin catalyst, the hexane can be recycled for the step (1) and also can be used for producing the polyolefin catalyst, and the precipitate can be used as a general solid waste treatment (titanium content 26 wt%, silicon content 10 wt% and phosphorus content 15 wt%).
Example 4
1) Firstly, replacing complete equipment of the thin film evaporator by nitrogen, and adding 500ml of titanium-containing filtrate into a metering bottle; opening a vacuum pump to vacuumize, adjusting a vacuum valve, and controlling the relative vacuum degree of the thin film evaporator to be-70 Kpa; introducing hot oil into a jacket of the thin film evaporator and gradually heating to 100 ℃; and (3) opening a feed valve, adding the titaniferous filtrate into a thin film evaporator, keeping the rotating speed of a scraper rotor constant, dispersing the titaniferous filtrate into a thin film (the thickness of the liquid film is 0.8cm, and the residence time is 3 minutes), and collecting distillate at the bottom of the evaporator to obtain titaniferous distillate.
2) 200mL of pentane was added to a 500mL glass reactor with mechanical stirring, reflux condenser and nitrogen protection, 50mL of a titanium-containing distillate was gradually added dropwise under stirring, and the mixture was stirred and mixed at room temperature for 2 hours, after the stirring was completed, a dark gray mixture was obtained, and a part of precipitate was visible. The mixture of the titanium-containing distillate and the organic solvent is cooled to 0 ℃, the mixture is kept stand and settled for 1 hour at the temperature, the settled precipitate and supernatant are subjected to solid-liquid separation, the earth gray precipitate (dry weight 15.5 g) is collected, 246ml of supernatant is further distilled to obtain 220ml of pentane solution containing titanium tetrachloride, the titanium tetrachloride content in the pentane solution containing titanium tetrachloride is 0.79 percent by weight, the distillation temperature is controlled to 130-136 ℃, and the purity of titanium tetrachloride is more than 98 percent after distillation. The titanium tetrachloride after rectification and purification can be used for producing a polyolefin catalyst, the pentane can be recycled in the step (1), the pentane can also be used for producing the polyolefin catalyst, and the precipitate can be used as a general solid waste treatment (the titanium content is 25 weight percent, the silicon content is 9 weight percent and the phosphorus content is 13.6 weight percent).
Example 5
1) Firstly, replacing complete equipment of the thin film evaporator by nitrogen, and adding 500ml of titanium-containing filtrate into a metering bottle; opening a vacuum pump to vacuumize, adjusting a vacuum valve, and controlling the relative vacuum degree of the thin film evaporator to be-70 Kpa; introducing hot oil into a jacket of the thin film evaporator and gradually heating to 100 ℃; and (3) opening a feed valve, adding the titaniferous filtrate into a thin film evaporator, keeping the rotating speed of a scraper rotor constant, dispersing the titaniferous filtrate into a thin film (the thickness of the liquid film is 0.5cm, and the residence time is 3 minutes), and collecting distillate at the bottom of the evaporator to obtain titaniferous distillate.
2) 200mL of octane was added to a 500mL glass reaction vessel with mechanical stirring, reflux condenser and nitrogen protection, 50mL of a titanium-containing distillate was gradually added dropwise under stirring, and the mixture was stirred and mixed at room temperature for 2 hours, after the stirring was completed, a dark gray mixture was obtained, and a part of precipitate was visible. The mixture of the titanium-containing distillate and the organic solvent is cooled to 0 ℃, the mixture is kept stand and settled for 1 hour at the temperature, the settled precipitate and supernatant are subjected to solid-liquid separation, the earth gray precipitate (dry weight 15.1 g) is collected, 246ml of supernatant is further distilled to obtain 220ml of octane solution containing titanium tetrachloride, the titanium tetrachloride content in the octane solution containing titanium tetrachloride is 0.78 weight percent, the distillation temperature is controlled to be 130-136 ℃, and the purity of titanium tetrachloride is more than 98 percent after distillation. The titanium tetrachloride after rectification and purification can be used for producing a polyolefin catalyst, the octane can be recycled for the step (1), the titanium tetrachloride can also be used for producing a polyolefin catalyst, and the precipitate can be used as a general solid waste treatment (the titanium content is 23 wt%, the silicon content is 8.9 wt% and the phosphorus content is 14 wt%).
Example 6
1) Firstly, replacing complete equipment of the thin film evaporator by nitrogen, and adding 500ml of titanium-containing filtrate into a metering bottle; opening a vacuum pump to vacuumize, adjusting a vacuum valve, and controlling the relative vacuum degree of the thin film evaporator to be-70 Kpa; introducing hot oil into a jacket of the thin film evaporator and gradually heating to 100 ℃; and (3) opening a feed valve, adding the titaniferous filtrate into a thin film evaporator, keeping the rotating speed of a scraper rotor constant, dispersing the titaniferous filtrate into a thin film (the thickness of the liquid film is 0.5cm, and the residence time is 3 minutes), and collecting distillate at the bottom of the evaporator to obtain titaniferous distillate.
2) 200mL of cyclohexane was added to a 500mL glass reactor with mechanical stirring, reflux condenser and nitrogen protection, 50mL of a titanium-containing distillate was gradually added dropwise under stirring, and the mixture was stirred and mixed at room temperature for 2 hours, after the stirring was completed, a dark gray mixture was obtained, and a part of precipitate was visible. The mixture of the titanium-containing distillate and the organic solvent is cooled to 0 ℃, the mixture is allowed to stand and settle for 1 hour at the temperature, the settled precipitate and supernatant are subjected to solid-liquid separation, the earth gray precipitate (dry weight 15.8 g) is collected, 246ml of supernatant is further distilled to obtain 220ml of cyclohexane solution containing titanium tetrachloride, the titanium tetrachloride content in the cyclohexane solution containing titanium tetrachloride is 0.77 weight percent, the distillation temperature is controlled to be 130-136 ℃, and the titanium tetrachloride with the purity of more than 98 percent is obtained after distillation. The titanium tetrachloride after rectification and purification can be used for producing a polyolefin catalyst, cyclohexane can be used for the step (1) and also can be used for producing a polyolefin catalyst, and the precipitate can be used as a general solid waste treatment (24 weight percent of titanium, 9.2 weight percent of silicon and 13.5 weight percent of phosphorus).
Example 7
1) Firstly, replacing complete equipment of the thin film evaporator by nitrogen, and adding 500ml of titanium-containing filtrate into a metering bottle; opening a vacuum pump to vacuumize, adjusting a vacuum valve, and controlling the relative vacuum degree of the thin film evaporator to be-70 Kpa; introducing hot oil into a jacket of the thin film evaporator and gradually heating to 100 ℃; and (3) opening a feed valve, adding the titaniferous filtrate into a thin film evaporator, keeping the rotating speed of a scraper rotor constant, dispersing the titaniferous filtrate into a thin film (the thickness of the liquid film is 0.5cm, and the residence time is 3 minutes), and collecting distillate at the bottom of the evaporator to obtain titaniferous distillate.
2) 200mL of cyclopentane was added to a 500mL glass reaction vessel with mechanical stirring, reflux condenser and nitrogen protection, 50mL of titanium-containing distillate was gradually added dropwise under stirring, and the mixture was stirred and mixed at room temperature for 2 hours, after the stirring was completed, a dark gray mixture was obtained, and a part of precipitate was visible. The mixture of the titanium-containing distillate and the organic solvent is cooled to 0 ℃, the mixture is allowed to stand and settle for 1 hour at the temperature, the settled precipitate and supernatant are subjected to solid-liquid separation, the earth gray precipitate (dry weight 15.6 g) is collected, 246ml of supernatant is further distilled to obtain 220ml of cyclopentane solution containing titanium tetrachloride, the titanium tetrachloride content in the cyclopentane solution containing titanium tetrachloride is 0.78% by weight, the distillation temperature is controlled to be 130-136 ℃, and the titanium tetrachloride with the purity of more than 98% is obtained after distillation. The titanium tetrachloride after rectification and purification can be used for producing a polyolefin catalyst, the cyclopentane can be recycled for the step (1), the titanium tetrachloride can also be used for producing a polyolefin catalyst, and the precipitate can be used as a general solid waste treatment (the titanium content is 23 wt%, the silicon content is 8.7 wt% and the phosphorus content is 12.7 wt%).
Comparative example 1
1) Firstly, replacing complete equipment of the thin film evaporator by nitrogen, and adding 500ml of titanium-containing filtrate into a metering bottle; opening a vacuum pump to vacuumize, adjusting a vacuum valve, and controlling the relative vacuum degree of the thin film evaporator to be-70 Kpa; introducing hot oil into a jacket of the thin film evaporator and gradually heating to 100 ℃; and (3) opening a feed valve, adding the titaniferous filtrate into a thin film evaporator, keeping the rotating speed of a scraper rotor constant, dispersing the titaniferous filtrate into a thin film (the thickness of the liquid film is 0.5cm, and the residence time is 3 minutes), and collecting distillate at the bottom of the evaporator to obtain titaniferous distillate.
2) 200mL of toluene was added to a 500mL glass reactor with mechanical stirring, reflux condenser and nitrogen protection, 50mL of a titanium-containing distillate was gradually added dropwise under stirring, and the mixture was stirred and mixed at room temperature for 2 hours, to give a dark gray mixture after the stirring was completed, and no precipitate appeared. And fully standing and settling the mixture of the titanium-containing distillate and the organic solvent after mixing, wherein the temperature is 0 ℃, the time is 1h, and no precipitate exists.
Comparative example 2
1) Firstly, replacing complete equipment of the thin film evaporator by nitrogen, and adding 500ml of titanium-containing filtrate into a metering bottle; opening a vacuum pump to vacuumize, adjusting a vacuum valve, and controlling the relative vacuum degree of the thin film evaporator to be-70 Kpa; introducing hot oil into a jacket of the thin film evaporator and gradually heating to 100 ℃; and (3) opening a feed valve, adding the titaniferous filtrate into a thin film evaporator, keeping the rotating speed of a scraper rotor constant, dispersing the titaniferous filtrate into a thin film (the thickness of the liquid film is 0.5cm, and the residence time is 3 minutes), and collecting distillate at the bottom of the evaporator to obtain titaniferous distillate.
2) 200mL of xylene was added to a 500mL glass reaction vessel with mechanical stirring, reflux condenser and nitrogen protection, 50mL of a titanium-containing distillate was gradually added dropwise under stirring, and the mixture was stirred and mixed at room temperature for 2 hours, to give a dark gray mixture after the stirring was completed, and no precipitate appeared. And fully standing and settling the mixture of the titanium-containing distillate and the organic solvent after mixing, wherein the temperature is 0 ℃, the time is 1h, and no precipitate exists.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (12)
1. A method for purifying nonmetallic impurities in a titanium-containing filtrate, the method comprising the steps of:
1) Evaporating the titaniferous filtrate through a thin film evaporator, and collecting bottom distillate to obtain titaniferous distillate;
2) Mixing the titanium-containing distillate with an inert organic solvent to obtain a mixture of the titanium-containing distillate and the inert organic solvent, wherein the inert organic solvent is one or more of alkane and cycloalkane;
3) Standing and settling the mixture obtained in the step 2), and carrying out solid-liquid separation on settled precipitate and supernatant;
4) Distilling and separating the supernatant obtained in the step 3) to obtain titanium tetrachloride and an organic solvent respectively,
wherein the titanium-containing filtrate is one or more than two of mother liquor and titanium treatment liquid generated in the preparation process of the ethylene polymerization catalyst,
the volume ratio of the inert organic solvent to the titanium-containing distillate is 3-6: 1, the temperature during standing is-10 ℃ to 0 ℃,
the cycloalkane is one or more of cyclopentane, cyclohexane, dimethylcyclopropane, ethylcyclopropane, methylcyclobutane and methylcyclopentane,
the alkane is one or more of pentane, hexane, heptane and octane.
2. The process according to claim 1, wherein the titanium tetrachloride obtained in step 4) is used for preparing an ethylene polymerization catalyst, and the organic solvent obtained in step 4) is used as the inert organic solvent.
3. The method of claim 1, wherein the titanium-containing filtrate is efficiently evaporated by a thin film evaporator to form a flowing liquid film on the inner wall of the evaporator, the thickness of the liquid film is less than 3cm, and the residence time is less than 5 minutes.
4. A method according to any one of claims 1-3, wherein the titanium-containing filtrate is subjected to reduced pressure distillation via a thin film evaporator, the conditions of the reduced pressure distillation comprising: the relative vacuum degree is-50 Kpa to-98 Kpa, and the temperature is 65-110 ℃.
5. A process according to any one of claims 1 to 3 wherein the titanium-containing filtrate contains toluene and titanium tetrachloride and the titanium-containing filtrate is efficiently evaporated by a thin film evaporator, toluene and part of the titanium tetrachloride forming a vapor stream is separated from the top and a titanium-containing distillate containing titanium tetrachloride and phosphorus and silicon compounds is obtained from the bottom.
6. A process according to any one of claims 1 to 3, wherein the temperature at the time of mixing is from-20 to 50 ℃ and the mixing time is from 0.1 to 10 hours.
7. A method according to any one of claims 1 to 3, wherein the time at rest after mixing is from 0.1 to 10h.
8. A process according to any one of claims 1 to 3 wherein the inert organic solvent content in the supernatant composition is 70 to 85% by weight and the titanium tetrachloride content is 15 to 30% by weight.
9. The method of claim 1, wherein the titanium tetrachloride and the organic solvent are separated by one or more of atmospheric distillation, vacuum distillation, atmospheric distillation, and vacuum distillation.
10. The method according to claim 1, wherein the titanium tetrachloride and the organic solvent are separated by distillation.
11. The method of claim 10, wherein the temperature of the rectification is 130-138 ℃.
12. A method according to any one of claims 1-3, wherein the solid-liquid separation is filtration and/or centrifugation.
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