CN113636595A - Method for recovering titanium-containing tower bottom liquid - Google Patents
Method for recovering titanium-containing tower bottom liquid Download PDFInfo
- Publication number
- CN113636595A CN113636595A CN202010346427.2A CN202010346427A CN113636595A CN 113636595 A CN113636595 A CN 113636595A CN 202010346427 A CN202010346427 A CN 202010346427A CN 113636595 A CN113636595 A CN 113636595A
- Authority
- CN
- China
- Prior art keywords
- titanium
- organic solvent
- inert organic
- titanium tetrachloride
- bottoms
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/001—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/28—Titanium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention relates to the field of polyolefin catalysts, and discloses a method for recovering titanium-containing tower bottoms. The method for recovering the titanium-containing tower bottoms comprises the following steps: 1) mixing the titanium-containing tower bottom liquid with an inert organic solvent to obtain a mixture of the titanium-containing tower bottom liquid and the inert organic solvent; 2) standing and settling the mixture obtained in the step 1), and carrying out solid-liquid separation on a precipitate and a supernatant fluid after standing and settling; 3) distilling and separating the supernatant obtained in the step 2) to respectively obtain titanium tetrachloride and an organic solvent. The method provided by the invention obviously improves the utilization rate of raw materials, greatly reduces the waste acid sludge generated in the treatment process, and greatly improves the recovery rate of titanium tetrachloride in the titanium-containing tower kettle liquid.
Description
Technical Field
The invention relates to the field of polyolefin catalysts, and particularly relates to a method for recovering titanium-containing tower bottoms.
Background
In the industrial production of polyolefin, titanium catalysts are widely used because of their high catalytic efficiency and low price. Chinese patent CN1718595A discloses a spherical catalyst component for olefin polymerization and a catalyst thereof, the spherical catalyst component comprises at least one titanium compound and optionally at least one electron donor compound supported on a magnesium halide active carrier, wherein the magnesium halide active carrier is solid particles obtained by rotating and dispersing a magnesium halide/alcohol adduct melt under a supergravity field. The catalyst has good particle morphology and narrow particle size distribution, has high polymerization activity and stereospecificity when being used for olefin polymerization, particularly propylene polymerization, and the obtained polymer has good particle morphology and high bulk density. In the above catalyst preparation process, it is usually necessary to wash the obtained solid catalyst primary particles with an organic solvent to remove titanium tetrachloride not carried therein, and a catalyst dispersion is discharged from the reactor, while producing a catalyst mother liquor of liquid-phase materials such as the organic solvent, titanium tetrachloride and chloroalkoxytitanium. In view of economic cost, the titanium tetrachloride and part of the organic solvent are recycled.
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 an organic solvent, titanium tetrachloride, chlorinated alkoxy titanium and the like into a mother liquor rough separation tower for rectification, obtaining the rough solvent from the tower top, obtaining titanium tetrachloride, chlorinated alkoxy titanium and the like from the tower bottom, separating the rough solvent and the chlorinated alkoxy titanium and the like respectively through an organic solvent rectification tower and a titanium tetrachloride rectification tower to obtain a required organic solvent and titanium tetrachloride product, feeding materials in the bottoms of the organic solvent rectification tower and the titanium tetrachloride rectification tower into rectification equipment for further rectification, discharging tower bottom liquid containing titanium tetrachloride and chlorinated alkoxy titanium from the rectification tower, discharging the tower bottom liquid containing titanium tetrachloride and chlorinated alkoxy titanium from a hydrolysis kettle for hydrolysis, and discharging generated waste 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 needed, so that increasingly serious environmental and economic pressures are faced.
In order to solve the problems, CN103030232A discloses a treatment method of titanium-containing waste liquid produced by polyolefin catalyst, and the invention belongs to the field of sewage treatment. Comprises the following process steps: (1) mixing titanium-containing waste liquid and water according to the weight ratio of 1: 0.5-1: 3, mixing, and carrying out hydrolysis treatment to obtain 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, so that the water quantity required by preparing alkali liquor in the conventional method is saved, the final waste treatment amount is reduced, the waste discharge is reduced, the final treatment product is solid waste, the solid waste can be further treated according to solid waste, the solid waste is convenient to transport compared with waste liquid, and the subsequent treatment mode can be treated by conventional means such as incineration, landfill and the like, so that the treatment cost is saved.
CN103028224A discloses a method for treating 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: the above configurationA good amount of lime milk is placed in the 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·nH20. According to the method, the lime milk is used as an alkali neutralizing agent, the titanium-containing waste liquid is directly subjected to hydrolysis neutralization reaction with the lime milk without hydrolysis reaction, so that the water consumption required by the conventional method is saved, the final treatment product is solid waste, the solid waste is convenient to transport, the subsequent treatment mode can be treated by conventional means such as incineration and landfill, and the treatment cost is saved.
Although the method reduces the generation of acid water to a certain extent, the obtained solid waste slag contains a large amount of organic matters, so that subsequent further treatment is obviously needed, and the treatment flow is complex.
Disclosure of Invention
The invention aims to provide a novel method for recovering titanium-containing tower bottom liquid, which obviously improves the utilization rate of raw materials, greatly reduces waste acid residues generated in the treatment process, greatly improves the recovery rate of titanium tetrachloride in the titanium-containing tower bottom liquid, and precipitates can be used for producing crude titanium dioxide, thereby realizing the resource recycling and having obvious environmental protection and economic benefits.
In order to achieve the above object, the present invention provides, in one aspect, a method for recovering titanium-containing bottoms, the method comprising the steps of:
1) mixing the titanium-containing tower bottom liquid with an inert organic solvent to obtain a mixture of the titanium-containing tower bottom liquid and the inert organic solvent;
2) standing and settling the mixture obtained in the step 1), and carrying out solid-liquid separation on a precipitate and a supernatant fluid after standing and settling;
3) distilling and separating the supernatant obtained in the step 2) to respectively obtain titanium tetrachloride and an organic solvent.
Preferably, the precipitate settled by standing in the step 2) is used for preparing crude titanium white, the titanium tetrachloride obtained in the step 3) is used for preparing the polyolefin catalyst, and the organic solvent obtained in the step 3) is used as the inert organic solvent.
Preferably, in the step 1), the volume ratio of the inert organic solvent to the titanium-containing tower bottoms in mixing is 0.1-10: 1.
preferably, the inert organic solvent is one or more of alkane having 5 to 12 carbon atoms and substituted or unsubstituted cycloalkane having 5 to 12 carbon atoms; more preferably, the inert organic solvent is one or more selected from the group consisting of cyclopentane, cyclohexane, dimethylcyclopropane, ethylcyclopropane, methylcyclobutane, methylcyclopentane, pentane, hexane, heptane, octane, nonane and decane.
Preferably, in step 2), the conditions for standing and settling comprise: the temperature is-20 to 50 ℃, and the time is 0.1 to 10 hours.
Preferably, in step 2), the solid-liquid separation is performed by filtration and centrifugation.
Preferably, in step 3), the distillation conditions include: the temperature is 90-130 ℃, and the vacuum degree is-30 to-98 Kpa.
Preferably, the method further comprises using the residue obtained by distillation in step 3) as the titanium-containing tower bottoms.
Preferably, the titanium-containing tower bottom liquid is tower bottom liquid obtained by distilling titanium tetrachloride of titanium-based polyolefin catalyst mother liquid to remove at least part of titanium tetrachloride.
Preferably, the titanium tetrachloride content of the titanium-containing tower bottoms may be, for example, 60 to 80 wt.%.
According to the recovery method of the titanium-containing tower bottom liquid provided by the invention, the precipitate settled by standing in the step 2) can be used for preparing crude titanium dioxide, the titanium tetrachloride obtained in the step 3) can be used for preparing a polyolefin catalyst, the organic solvent obtained in the step 3) can be used as the inert organic solvent, and then the residue obtained by distillation in the step 3) can be used as the titanium-containing tower bottom liquid, so that the utilization rate of raw materials is obviously improved, the waste acid residues generated in the treatment process are greatly reduced, the recovery rate of the titanium tetrachloride in the titanium-containing tower bottom liquid is greatly improved, and the precipitate can be used for producing the crude titanium dioxide, so that the resource recovery and utilization are realized, and the recovery method has obvious environmental protection and economic benefits.
Detailed Description
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.
The invention provides a method for recovering titanium-containing tower bottoms, which comprises the following steps:
1) mixing the titanium-containing tower bottom liquid with an inert organic solvent to obtain a mixture of the titanium-containing tower bottom liquid and the inert organic solvent;
2) standing and settling the mixture obtained in the step 1), and carrying out solid-liquid separation on a precipitate and a supernatant fluid after standing and settling;
3) distilling and separating the supernatant obtained in the step 2) to respectively obtain titanium tetrachloride and an organic solvent.
According to the present invention, it is preferable that the precipitate settled by standing in the step 2) is used for preparing a crude titanium white, the titanium tetrachloride obtained in the step 3) is used for preparing a polyolefin catalyst, and the organic solvent obtained in the step 3) is used as the inert organic solvent.
According to the invention, the tower bottom liquid is the tower bottom liquid obtained by distilling the titanium-based polyolefin catalyst mother liquid to remove at least part of titanium tetrachloride.
The titanium-containing tower bottoms are a mixture containing titanium tetrachloride, chloroalkoxytitanium, and the like. The titanium tetrachloride content of the titanium-containing tower bottoms may be, for example, 60 to 80 wt.%. The content of the chloroalkoxytitanium may be, for example, 20 to 40% by weight.
When a titanium tetrachloride is partially distilled off from the titanium-based polyolefin catalyst mother liquor, the amount of titanium tetrachloride to be removed may be such that the remaining titanium tetrachloride content is in the above range.
According to the invention, the titanium-containing tower bottoms are mixed with an inert organic solvent to obtain a mixture of the titanium-containing tower bottoms and the inert organic solvent. The amount of the inert organic solvent can be determined according to the amount of the titanium-containing tower bottoms, and in view of effectively improving the utilization rate of the titanium-containing tower bottoms, in step 1), the volume ratio of the inert organic solvent to the titanium-containing tower bottoms in mixing is preferably 0.1-10: 1; more preferably, the volume ratio of the inert organic solvent to the titanium-containing tower bottoms in mixing is 1-6: 1.
the method for mixing the titanium-containing tower bottoms with the inert organic solvent is not particularly limited, and the titanium-containing tower bottoms can be firstly added into a mixing container, and then the inert organic solvent is added for mixing; or adding an inert organic solvent and then adding the titanium-containing tower bottoms for mixing; preferably, the inert organic solvent is added into the mixing container, and then the titanium-containing tower bottoms are added for mixing. The mixing is preferably performed under stirring.
The mixing conditions preferably include: the temperature is-20 to 50 ℃, and the time is 0.1 to 10 hours. More preferably, the mixing conditions described above include: the temperature is-10 to 30 ℃, and the time is 0.5 to 5 hours.
In a preferred embodiment of the invention, the mixing is carried out in two stages, the first stage mixing is carried out at 10-40 ℃ for 1-3 hours, and the second stage mixing is carried out at-15-5 ℃ for 0.5-2 hours; preferably, the first stage mixing is carried out at 20-40 ℃ for 1.5-2.5 hours, and the second stage mixing is carried out at-10-0 ℃ for 0.5-1 hour.
According to the present invention, the inert organic solvent may be any organic solvent which does not react with each component in the titanium-containing bottom liquid, and preferably, the inert organic solvent is one or more of an alkane having 5 to 12 carbon atoms and a substituted or unsubstituted cycloalkane having 5 to 12 carbon atoms.
Specific examples of the inert organic solvent include: cycloalkanes such as cyclopentane, cyclohexane, dimethylcyclopropane, ethylcyclopropane, methylcyclobutane and methylcyclopentane, and alkanes having 5 to 12 carbon atoms such as pentane, hexane, heptane, octane, nonane and decane. The organic solvent can be used alone in 1, also can be used more than 2.
According to the invention, after the titanium-containing tower bottoms and the inert organic solvent are mixed, the mixture obtained by mixing is kept still for sedimentation, and solid-liquid separation is carried out on the precipitate and the supernatant liquid after the sedimentation.
Preferably, in step 2), the conditions for standing and settling comprise: the temperature is-20 to 50 ℃, and the time is 0.1 to 10 hours; more preferably, the mixing conditions described above include: the temperature is-10 to 30 ℃, and the time is 0.5 to 5 hours; further preferably, the mixing conditions include: the temperature is-10 to 0 ℃, and the time is 0.5 to 1.5 hours. In addition, it is preferable that the temperature of the standing sedimentation is the same as the temperature at the end of the mixing, that is, it is preferable that the standing sedimentation is performed at the temperature at the end of the mixing.
According to the present invention, after the standing sedimentation, a precipitate of the standing sedimentation and a supernatant are obtained by solid-liquid separation. The solid-liquid separation may be carried out by various methods generally used in the art, and for example, the solid-liquid separation may be carried out by filtration or centrifugation. The filtration may be, for example, filter pressing, suction filtration, atmospheric filtration, membrane filtration, or the like.
The precipitate obtained by solid-liquid separation and standing and settling contains chloroalkoxytitanium, the content of chloroalkoxytitanium is more than 90 wt%, and crude titanium white with high purity can be extracted by further processing and separating to remove chloroalkoxy groups, so that the precipitate can be used for preparing the crude titanium white. The titanium content of the chloroalkoxytitanium may be, for example, 20 to 30% by weight.
According to the invention, titanium tetrachloride and the organic solvent are respectively obtained by distilling and separating the supernatant obtained in the step 2). Preferably, the conditions of the distillation include: the temperature is 90-130 ℃, and the vacuum degree is-30 to-98 Kpa; more preferably, the conditions of the distillation include: the temperature is 90-120 ℃, and the vacuum degree is-30 to-85 Kpa.
In view of further effectively improving the utilization rate of the titanium-containing tower bottoms according to the present invention, it is preferable that the method further comprises using the residue obtained by distillation in step 3) as the titanium-containing tower bottoms.
In the invention, the precipitate obtained by standing and settling is used for preparing the crude titanium dioxide, the titanium tetrachloride obtained by distillation is used for preparing the polyolefin catalyst, the organic solvent obtained by distillation is used as the inert organic solvent, and the residue obtained by distillation is used as the titanium-containing tower kettle liquid, so that the utilization rate of raw materials is obviously improved, the acid sludge generated in the treatment process is greatly reduced, the recovery rate of the titanium tetrachloride in the titanium-containing tower kettle liquid is greatly improved, and the precipitate can be used for producing the crude titanium dioxide, thereby realizing the resource recycling and having obvious environmental protection and economic benefits.
The present invention will be described in detail below by way of examples, but the present invention is not limited to the following examples.
In the following examples, the titanium-containing tower bottoms is the tower bottoms obtained by removing part of titanium tetrachloride from the titanium-based polyolefin catalyst mother liquor by atmospheric distillation, and mainly comprises: the titanium tetrachloride content was 70% by weight, the remainder being mainly chlorinated titanium alkoxides.
Example 1
This example illustrates the recovery of titanium containing bottoms.
250mL of inert organic solvent (hexane) was added to a 500mL glass reactor equipped with mechanical stirring, reflux condenser and nitrogen blanket, 50mL of titanium-containing column bottoms were gradually added with stirring, stirred and mixed at room temperature (25 ℃) for 2 hours, and after stirring was completed, a dark gray mixture was obtained, with some precipitation being visible. Freezing the mixture of titanium-containing tower bottom liquid and hexane under stirring for precipitation at-10 deg.C for 0.5h, standing at-10 deg.C for precipitation for 1.5h, filtering the precipitate and supernatant, collecting grayish precipitate (90 wt% of chloroalkoxytitanium, wherein the titanium content is 21 wt%), and further distilling the supernatant to obtain hexane solution containing titanium tetrachloride, wherein the distillation temperature is 110 deg.C and the vacuum degree is-85 Kpa. The hexane solution containing titanium tetrachloride was further subjected to rectification to obtain titanium tetrachloride and hexane. The purified titanium tetrachloride is used for the production of a polyolefin catalyst, hexane is used as an inert organic solvent for the next recovery, the distillation residue is used for the next recovery together with the titanium-containing tower bottoms, and the precipitate is used for the production of crude titanium dioxide.
Example 2
This example illustrates the recovery of titanium containing bottoms.
250mL of inert organic solvent (hexane) was added to a 500mL glass reactor equipped with mechanical stirring, reflux condenser and nitrogen blanket, 50mL of titanium-containing column bottoms were gradually added with stirring, stirred and mixed at room temperature (25 ℃) for 2 hours, and after stirring was completed, a dark gray mixture was obtained, with some precipitation being visible. Freezing the mixture of titanium-containing tower bottoms and hexane under stirring at 0 deg.C for 1 hr, standing at 0 deg.C for 1 hr, filtering the precipitate and supernatant, collecting grayish precipitate (containing 93 wt% of chloroalkoxytitanium and 24 wt% of titanium), and further distilling the supernatant to obtain hexane solution containing titanium tetrachloride at 105 deg.C and-75 Kpa. The hexane solution containing titanium tetrachloride was further subjected to rectification to obtain titanium tetrachloride and hexane. The purified titanium tetrachloride is used for the production of a polyolefin catalyst, hexane is used as an inert organic solvent for the next recovery, the distillation residue is used for the next recovery together with the titanium-containing tower bottoms, and the precipitate is used for the production of crude titanium dioxide.
Example 3
This example illustrates the recovery of titanium containing bottoms.
250mL of inert organic solvent (hexane) was added to a 500mL glass reactor equipped with mechanical stirring, reflux condenser and nitrogen blanket, 50mL of titanium-containing column bottoms were gradually added with stirring, stirred and mixed at room temperature (25 ℃) for 2 hours, and after stirring was completed, a dark gray mixture was obtained, with some precipitation being visible. Freezing the mixture of titanium-containing tower bottom liquid and hexane under stirring for precipitation at-5 deg.C for 0.5 hr, standing at-5 deg.C for precipitation for 0.5 hr, filtering the precipitate and supernatant, collecting grayish precipitate (chloralkoxytitanium content of 91 wt%, titanium content of 25 wt%), and further distilling the supernatant to obtain hexane solution containing titanium tetrachloride, wherein the distillation temperature is 100 deg.C and vacuum degree is-70 Kpa. The hexane solution containing titanium tetrachloride was further subjected to rectification to obtain titanium tetrachloride and hexane. The purified titanium tetrachloride is used for the production of a polyolefin catalyst, hexane is used as an inert organic solvent for the next recovery, the distillation residue is used for the next recovery together with the titanium-containing tower bottoms, and the precipitate is used for the production of crude titanium dioxide.
Example 4
The procedure is as in example 1, except that 100ml of an inert organic solvent is used. The purified titanium tetrachloride was used for the production of a polyolefin catalyst, hexane was used as an inert organic solvent for the next recovery, the distillation residue was used for the next recovery together with the titanium-containing column bottoms, and the precipitate (titanium chloroalkoxide content 95% by weight, titanium content 28% by weight) was used for the production of crude titanium white.
Example 5
The procedure of example 1 was followed except that the inert organic solvent was octane, the supernatant was further distilled under conditions of a distillation temperature of 100 ℃ and a vacuum degree of-80 Kpa to obtain an octane solution containing titanium tetrachloride, and the octane solution containing titanium tetrachloride was further rectified to obtain titanium tetrachloride and octane. The purified titanium tetrachloride was used for the production of a polyolefin catalyst, octane was used for the next recovery as an inert organic solvent, the distillation residue was used for the next recovery together with the titanium-containing column bottoms, and the precipitate (chloroalkoxytitanium content of 90% by weight, wherein the titanium content was 29% by weight) was used for the production of crude titanium white.
Example 6
The procedure of example 1 was followed except that decane was used as the inert organic solvent, and the supernatant was further distilled under conditions such that the distillation temperature was 120 ℃ and the degree of vacuum was-85 Kpa to obtain a decane solution containing titanium tetrachloride, which was further subjected to rectification to obtain titanium tetrachloride and decane. The purified titanium tetrachloride was used for the production of a polyolefin catalyst, decane was used as an inert organic solvent for the next recovery, the distillation residue was used for the next recovery together with the titanium-containing column bottoms, and the precipitate (titanium chloroalkoxide content 94% by weight, titanium content 27% by weight) was used for the production of crude titanium white.
Example 7
The procedure of example 1 was followed except that the inert organic solvent was cyclohexane, the supernatant was further distilled under conditions of a distillation temperature of 120 ℃ and a vacuum degree of-60 Kpa to obtain a cyclohexane solution containing titanium tetrachloride, and the cyclohexane solution containing titanium tetrachloride was further rectified to obtain titanium tetrachloride and cyclohexane. The purified titanium tetrachloride was used for the production of a polyolefin catalyst, cyclohexane was used as an inert organic solvent for the next recovery, the distillation residue was used for the next recovery together with the titanium-containing column bottoms, and the precipitate (chloroalkoxytitanium content 95% by weight, titanium content 22% by weight) was used for the production of crude titanium white.
Example 8
The procedure of example 1 was followed except that ethyl cyclopropane was used as the inert organic solvent, the supernatant was further distilled under conditions of a distillation temperature of 90 ℃ and a degree of vacuum of-30 Kpa to obtain an ethyl cyclopropane solution containing titanium tetrachloride, and the ethyl cyclopropane solution containing titanium tetrachloride was further rectified to obtain titanium tetrachloride and ethyl cyclopropane. The purified titanium tetrachloride was used for the production of a polyolefin catalyst, ethylcyclopropane was used for the next recovery as an inert organic solvent, the distillation residue was used for the next recovery together with the titanium-containing column bottoms, and in addition, the precipitate (chloroalkoxytitanium content of 97% by weight, wherein the titanium content was 25% by weight) was used for the production of crude titanium white.
Example 9
The procedure of example 1 was followed except that dimethyl cyclopropane was used as the inert organic solvent, and the supernatant was further distilled under conditions of a distillation temperature of 90 ℃ and a degree of vacuum of-30 Kpa to obtain a dimethyl cyclopropane solution containing titanium tetrachloride, and the dimethyl cyclopropane solution containing titanium tetrachloride was further subjected to rectification to obtain titanium tetrachloride and dimethyl cyclopropane. The purified titanium tetrachloride was used for the production of a polyolefin catalyst, dimethylcyclopropane was used for the next recovery as an inert organic solvent, the distillation residue was used for the next recovery together with the titanium-containing column bottoms, and in addition, the precipitate (chloroalkoxytitanium content of 97% by weight, wherein the titanium content was 25% by weight) was used for the production of crude titanium white.
Example 10
The procedure of example 1 was followed except that methylcyclopentane was used as the inert organic solvent, the supernatant was further distilled under conditions of a distillation temperature of 90 ℃ and a degree of vacuum of-50 Kpa to obtain a methylcyclopentane solution containing titanium tetrachloride, and the methylcyclopentane solution containing titanium tetrachloride was further subjected to rectification to obtain titanium tetrachloride and methylcyclopentane. The purified titanium tetrachloride was used for the production of a polyolefin catalyst, methylcyclopentane was used as an inert organic solvent for the next recovery, the distillation residue was used for the next recovery together with the titanium-containing column bottoms, and in addition, the precipitate (chloroalkoxytitanium content 93% by weight, wherein the titanium content was 23% by weight) was used for the production of crude titanium white.
Example 11
The procedure of example 1 was followed except that methylcyclopentane was used as the inert organic solvent, the supernatant was further distilled under conditions of a distillation temperature of 100 ℃ and a degree of vacuum of-50 Kpa to obtain a methylcyclopentane solution containing titanium tetrachloride, and the methylcyclopentane solution containing titanium tetrachloride was further subjected to rectification to obtain titanium tetrachloride and methylcyclopentane. The purified titanium tetrachloride was used for the production of a polyolefin catalyst, methylcyclopentane was used as an inert organic solvent for the next recovery, the distillation residue was used for the next recovery together with the titanium-containing column bottoms, and in addition, the precipitate (chloroalkoxytitanium content 97% by weight, wherein the titanium content was 26% by weight) was used for the production of crude titanium white.
Example 12
The procedure is as in example 1, except that 50ml of the titanium-containing bottoms are replaced by 25ml of the distillation residue obtained in example 1 and 25ml of the titanium-containing bottoms. The purified titanium tetrachloride was used for the production of a polyolefin catalyst, octane was used for the next recovery as an inert organic solvent, the distillation residue was used for the next recovery together with the titanium-containing column bottoms, and in addition, the precipitate (chloroalkoxytitanium content of 90% by weight, wherein the titanium content was 30% by weight) was used for the production of crude titanium white.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. A method for recovering titanium-containing tower bottoms is characterized by comprising the following steps:
1) mixing the titanium-containing tower bottom liquid with an inert organic solvent to obtain a mixture of the titanium-containing tower bottom liquid and the inert organic solvent;
2) standing and settling the mixture obtained in the step 1), and carrying out solid-liquid separation on a precipitate and a supernatant fluid after standing and settling;
3) distilling and separating the supernatant obtained in the step 2) to respectively obtain titanium tetrachloride and an organic solvent.
2. The recovery method according to claim 1, wherein the precipitate settled by standing in the step 2) is used for producing crude titanium white, the titanium tetrachloride obtained in the step 3) is used for producing a polyolefin catalyst, and the organic solvent obtained in the step 3) is used as the inert organic solvent.
3. The recovery method according to claim 1, wherein in the step 1), the volume ratio of the inert organic solvent to the titanium-containing tower bottoms is 0.1-10: 1.
4. the recovery method according to claim 1, wherein the inert organic solvent is one or more of a paraffin having 5 to 12 carbon atoms and a substituted or unsubstituted cycloalkane having 5 to 12 carbon atoms.
5. The recovery method according to any one of claims 1 to 3, wherein the inert organic solvent is one or more selected from cyclopentane, cyclohexane, dimethylcyclopropane, ethylcyclopropane, methylcyclobutane, methylcyclopentane, pentane, hexane, heptane, octane, nonane and decane.
6. The recovery method according to any one of claims 1 to 3, wherein the conditions of the still standing sedimentation in step 2) include: the temperature is-20 to 50 ℃, and the time is 0.1 to 10 hours.
7. The recovery method according to any one of claims 1 to 3, wherein in step 2), the solid-liquid separation is performed by filtration or centrifugation.
8. A recovery process according to any one of claims 1 to 3, wherein in step 3) the distillation conditions comprise: the temperature is 90-130 ℃, and the vacuum degree is-30 to-98 Kpa.
9. The recovery method according to any one of claims 1 to 3, further comprising using the residue obtained by distillation in step 3) as the titanium-containing bottoms.
10. The recovery method according to any one of claims 1 to 3, wherein the titanium-containing bottoms is a bottoms obtained by distilling a titanium-based polyolefin catalyst mother liquor to remove at least part of titanium tetrachloride.
11. A recovery process as claimed in claim 9, wherein the titanium tetrachloride content of the titanium-containing tower bottoms is for example 60-80% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010346427.2A CN113636595A (en) | 2020-04-27 | 2020-04-27 | Method for recovering titanium-containing tower bottom liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010346427.2A CN113636595A (en) | 2020-04-27 | 2020-04-27 | Method for recovering titanium-containing tower bottom liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113636595A true CN113636595A (en) | 2021-11-12 |
Family
ID=78415289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010346427.2A Pending CN113636595A (en) | 2020-04-27 | 2020-04-27 | Method for recovering titanium-containing tower bottom liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113636595A (en) |
Citations (6)
| 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 |
| US5948212A (en) * | 1996-10-21 | 1999-09-07 | Union Carbide Chemicals & Plastics Technology Corporation | Titanium separation process |
| CN103420413A (en) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | Method of recycling refined titanium tetrachloride from titanium-containing waste liquid |
| 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 |
| CN104129812A (en) * | 2013-05-03 | 2014-11-05 | 中国石油化工股份有限公司 | Treatment method of titanium-containing waste solution |
| CN105502515A (en) * | 2016-01-18 | 2016-04-20 | 重庆科技学院 | Method for comprehensively recycling polymeric ferric aluminum chloride from titanium tetrachloride precipitate slurry |
-
2020
- 2020-04-27 CN CN202010346427.2A patent/CN113636595A/en active Pending
Patent Citations (6)
| 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 |
| US5948212A (en) * | 1996-10-21 | 1999-09-07 | Union Carbide Chemicals & Plastics Technology Corporation | Titanium separation process |
| CN103420413A (en) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | Method of recycling refined titanium tetrachloride from titanium-containing waste liquid |
| 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 |
| CN104129812A (en) * | 2013-05-03 | 2014-11-05 | 中国石油化工股份有限公司 | Treatment method of titanium-containing waste solution |
| CN105502515A (en) * | 2016-01-18 | 2016-04-20 | 重庆科技学院 | Method for comprehensively recycling polymeric ferric aluminum chloride from titanium tetrachloride precipitate slurry |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101065506B (en) | Method for recovering titanium tetrachloride from a waste liquid | |
| CN101698639B (en) | Method for recycling sodium formate products from coarse sodium formate of byproduct of polyhydric alcohol | |
| CN113636595A (en) | Method for recovering titanium-containing tower bottom liquid | |
| CN112707437A (en) | Treatment method of titanium tetrachloride-containing waste liquid | |
| CN112707435A (en) | Method for recovering refined titanium tetrachloride from titanium tetrachloride-containing waste liquid | |
| CN113636593B (en) | Recovery method for titanium-containing tower kettle liquid | |
| CN112707556A (en) | Titanium-containing waste liquid treatment method and titanium-containing dry powder | |
| CN113636594B (en) | Recovery method for mother solution containing titanium tetrachloride | |
| CN113636591B (en) | Method for purifying nonmetallic impurities in titaniferous filtrate | |
| CN113636590B (en) | Method for purifying nonmetallic impurities in titanium-containing filtrate | |
| CN112239226A (en) | Method for treating titanium-containing waste liquid generated in production process of polyolefin catalyst | |
| CN112707532B (en) | Treatment method of titanium-containing distillation residual liquid, titanium white raw material and application | |
| CN113636906B (en) | Purifying method of titanium-containing filtrate | |
| CN112704894A (en) | Catalyst solvent recovery method and titanium-containing solid | |
| CN112707449B (en) | Method for treating titanium-containing waste liquid | |
| CN112723580A (en) | Method for reducing chlorine content in chlorine-containing organic waste liquid and method for treating chlorine-containing organic waste liquid | |
| CN112708782B (en) | Titanium-containing waste liquid treatment method and titanium-containing dry powder | |
| CN112707559B (en) | Treatment method of titanium-containing distillation raffinate | |
| CN112707530B (en) | Treatment method of titanium-containing distillation residual liquid | |
| CN114426306B (en) | Titanium polyolefin catalyst mother liquor treatment device and method | |
| CN112707560B (en) | Treatment method of titanium-containing waste liquid, titanium dioxide raw material and application | |
| CN112239224A (en) | Method for recovering titanium tetrachloride | |
| CN112707557B (en) | Treatment method of titanium-containing waste liquid | |
| CN115057568B (en) | Method for treating ammonium paratungstate crystallization mother liquor | |
| CN112707561B (en) | Treatment method of titanium-containing waste liquid |
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 |