CN112707530B - Treatment method of titanium-containing distillation residual liquid - Google Patents
Treatment method of titanium-containing distillation residual liquid Download PDFInfo
- Publication number
- CN112707530B CN112707530B CN201911015057.8A CN201911015057A CN112707530B CN 112707530 B CN112707530 B CN 112707530B CN 201911015057 A CN201911015057 A CN 201911015057A CN 112707530 B CN112707530 B CN 112707530B
- Authority
- CN
- China
- Prior art keywords
- titanium
- containing distillation
- alcohol
- distillation residue
- liquid
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1456—Removing acid components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/38—Polymers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention belongs to the field of industrial waste liquid treatment, and relates to a treatment method of titanium-containing distillation raffinate. The titanium-containing distillation residual liquid is titanium tetrachloride-containing distillation residual liquid generated in the preparation process of a titanium polyolefin catalyst, and the method comprises the following steps: (1) Mixing the titanium-containing distillation residual liquid with an alcohol compound for alcoholysis reaction to obtain an alcoholysis product containing hydrogen chloride; (2) Directly carrying out solid-liquid separation on the alcoholysis product obtained in the step (1), or carrying out neutralization reaction on the alcoholysis product and an alkaline substance, and then carrying out solid-liquid separation to obtain an organic waste liquid and solid waste residue. The method can obviously shorten the treatment process, greatly reduce the waste water and the waste residues generated in the treatment process of the titanium-containing distillation residue, greatly reduce the chlorine content in the waste liquid, can be directly incinerated, and has obvious environmental protection and economic benefits.
Description
Technical Field
The invention belongs to the field of industrial waste liquid treatment, and particularly relates to a treatment method of titanium-containing distillation raffinate.
Background
In the industrial production of polyolefin, titanium catalysts are widely used due to high catalytic efficiency and low price. One common method of preparing such catalysts is currently: the preparation of the magnesium solution is first carried out, for example, by preparing a magnesium solution by reacting magnesium or a magnesium compound with a relevant solvent in the presence of a hydrocarbon assistant, and then reacting the magnesium solution with a halogen-containing compound such as titanium tetrachloride to prepare a magnesium-supported catalyst, during which various promoters may be added for modification. In the above catalyst preparation process, it is usually necessary to wash the obtained solid catalyst component with a hydrocarbon solvent to remove titanium tetrachloride not carried therein, and a catalyst slurry is discharged from the reactor, while producing a catalyst mother liquor containing a liquid-phase material such as a hydrocarbon solvent, titanium tetrachloride and high boiling substances.
The recycling process of the polyolefin catalyst mother liquor which is industrialized at home at present is approximately as follows: the method comprises the steps of firstly feeding a mother liquor mixture containing a hydrocarbon solvent, titanium tetrachloride and high-boiling residues into a mother liquor rough separation tower for distillation, obtaining the crude solvent at the tower top, obtaining titanium tetrachloride and high-boiling residues at the tower bottom, then 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 products, feeding the material at the tower bottom of the hydrocarbon solvent rectifying tower and the material at the tower bottom of the titanium tetrachloride rectifying tower into a dry distillation kettle for further distillation, and discharging residual liquid containing the titanium tetrachloride and the high-boiling residues discharged from the dry distillation kettle as waste water and waste residues after hydrolysis in a water washing kettle and neutralization with alkali. The process has the following problems: 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.
In order to solve the above problems, CN201110303198.7 discloses a treatment method of titanium-containing waste liquid produced by polyolefin catalyst, comprising the following process steps: (1) mixing the titanium-containing waste liquid with water according to the weight ratio of 1:0.5 to 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 to control Ca (OH) 2 Ratio of powder to original titanium-containing waste liquid to make Ca (OH) 2 The powder reacts with the hydrolysate to form solid residues. The invention adopts solid lime Ca (OH) 2 The powder is used as an alkali neutralizer, and the final treatment product is solid waste residue.
CN201110303200.0 discloses a method for treating titanium-containing waste liquid, which comprises the following process steps: slaked lime (Ca (OH) 2 ) Preparing lime milk in a lime milk storage tank according to a certain proportion with water: placing a certain amount of lime milk prepared 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 TiO 2 /CaCl 2 ·nH 2 O。
Although the production of acid water is reduced to a certain extent in the prior art, 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 for treating the titanium-containing distillation raffinate based on a brand-new thought, so that the treatment process can be obviously shortened, the waste water and the waste residues generated in the treatment process of the titanium-containing distillation raffinate can be greatly reduced, the chlorine content in the waste liquor can be greatly reduced, the waste liquor can be directly incinerated, and the method has obvious environmental protection and economic benefits.
In order to achieve the above object, the present invention provides a method for treating a titanium-containing distillation residue, which is a titanium tetrachloride-containing distillation residue produced in the production of a titanium-based polyolefin catalyst, comprising the steps of:
(1) Mixing the titanium-containing distillation residual liquid with an alcohol compound for alcoholysis reaction to obtain an alcoholysis product containing hydrogen chloride;
(2) Directly carrying out solid-liquid separation on the alcoholysis product obtained in the step (1), or carrying out neutralization reaction on the alcoholysis product and an alkaline substance, and then carrying out solid-liquid separation to obtain an organic waste liquid and solid waste residue.
Compared with the prior art that titanium-containing distillation raffinate is treated by water so as to generate a large amount of wastewater containing organic matters and titanium dioxide, the method adopts alcohol compounds to treat the titanium-containing distillation raffinate, reaction products are mixtures of inflammable alkoxy titanium and other organic matters, after solid-liquid separation, the chlorine content of the organic wastewater is reduced, the organic wastewater can be directly incinerated, and the problem that acid-containing wastewater generated in the prior art is difficult to treat is really solved. Preferably, the alcoholysis product and the alkaline substance can also be subjected to neutralization reaction, and hydrogen chloride contained in the alcoholysis product is removed to further reduce the chlorine content in the waste liquid. The method can greatly reduce the corrosion to treatment equipment and secondary pollution such as dioxin and the like possibly generated in the incineration process, and has obvious environmental protection and economic benefits.
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 preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
The invention provides a method for treating titanium-containing distillation residual liquid, which is titanium tetrachloride-containing distillation residual liquid generated in the preparation process of a titanium polyolefin catalyst, and comprises the following steps:
(1) Mixing the titanium-containing distillation residual liquid with an alcohol compound for alcoholysis reaction to obtain an alcoholysis product containing hydrogen chloride;
(2) Directly carrying out solid-liquid separation on the alcoholysis product obtained in the step (1), or carrying out neutralization reaction on the alcoholysis product and an alkaline substance, and then carrying out solid-liquid separation to obtain an organic waste liquid and solid waste residue.
The term "distillation residue containing titanium tetrachloride which is the object of the present invention, i.e., the distillation residue containing titanium tetrachloride produced in the production of a titanium-based polyolefin catalyst, is known to those skilled in the art, and means a residue containing titanium tetrachloride and high boiling components which is obtained by distilling a part of titanium tetrachloride from a catalyst mother liquor produced in the production of a titanium-based polyolefin catalyst.
Although the different processes may differ slightly in the preparation conditions, so that the composition and content of the titanium-containing distillation residue are slightly different, they do not constitute an influence on the post-treatment step. The method is suitable for all the distillation residual liquid containing titanium tetrachloride generated in the preparation process of the titanium polyolefin catalyst.
In the present invention, the alcohol compound may be at least one of a monohydric alcohol, a dihydric alcohol and a polyhydric alcohol.
Specifically, the monohydric alcohol is preferably at least one alcohol compound represented by the general formula ROH, wherein R is C 1 -C 12 Linear or branched alkyl of (2), C 3 -C 12 Cycloalkyl or C 7 -C 12 Aralkyl group of (1); the monohydric alcohol is further preferably at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, cyclopentanol, benzyl alcohol, and benzyl alcohol.
Specifically, the diol is preferably C 2 -C 12 The dihydric alcohol of (1); further preferred is ethylene glycol and/or propylene glycol.
Specifically, the polyol is preferably C 2 -C 12 The trihydric alcohol of (1); further excellenceIs selected as glycerol.
In the invention, the adding amount of the alcohol compound is determined according to the volume of the titanium-containing distillation residual liquid to be treated, and the using amount of the alcohol compound is reduced as much as possible on the premise of meeting the requirement of alcoholysis reaction. Preferably, the volume ratio of the alcohol compound to the titanium-containing distillation residual liquid is 0.05-15: 1, preferably 0.1 to 10:1, more preferably 0.2 to 5:1.
according to a specific processing method of the invention: firstly, obtaining the total volume of materials which can be processed according to the actual capacity of a reaction kettle, and then obtaining the corresponding addition of alcohol compounds and titanium-containing distillation residual liquid according to the conversion of the volume.
According to the present invention, in order to achieve better alcoholysis effect, preferably, in step (1), the alcoholysis reaction is carried out under stirring conditions, and the temperature of the alcoholysis reaction is not higher than the boiling point of the alcohol compound.
Similar to the hydrolysis process of the prior art, HCl gas is also generated during alcoholysis, preferably step (1) further comprises: absorbing HCl gas generated in the alcoholysis reaction process. Specifically, the HCl gas generated during the alcoholysis reaction may be neutralized and absorbed using conventional methods, for example, by absorbing the HCl gas generated during the alcoholysis reaction with water or an alkaline substance. The alkaline substance may be a common variety of alkaline substances for neutralization, such as sodium hydroxide.
In a specific alcoholysis reaction, the titanium-containing distillation residue can be added into a kettle, and then an alcohol compound is added (namely, the alcohol compound is added into the titanium-containing distillation residue); or adding the alcohol compound first and then adding the titanium-containing distillation residual liquid (namely, adding the titanium-containing distillation residual liquid into the alcohol compound); preferably, the alcohol compound is added to the titanium-containing distillation residue.
According to the method of the present invention, the basic substance is added in step (2) in order to neutralize the hydrogen chloride in the alcoholysis solution, and therefore, various neutralizing bases conventional in the art, for example, hydroxides and/or oxides of alkali metals and/or alkaline earth metals; specifically, at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide, and calcium oxide may be preferred. The purpose of the neutralization is to reduce the corrosion of chloride to subsequent treatment equipment, and therefore, the addition amount of the alkaline substance is preferably to neutralize the alcoholysis solution to be neutral or weakly alkaline.
In the present invention, the neutralization conditions are not particularly limited, the temperature can be selected from the range of normal temperature to the boiling point of the solvent, and the addition form of the basic substance is preferably solid, and therefore, in order to accelerate the dissolution thereof, the neutralization reaction is preferably carried out at a relatively high temperature in an optional range.
The method for solid-liquid separation is not particularly limited in the present invention, and the purpose of solid-liquid separation can be achieved. Specifically, the separation method can be at least one selected from sedimentation separation, filtration separation, filter-press separation, vacuum separation, centrifugal separation and spray-drying separation.
According to the method, the organic waste liquid can be directly subjected to incineration treatment, and the incineration treatment can be carried out by adopting a conventional treatment mode meeting the environmental protection regulations. The solid waste can be treated according to the conventional solid waste treatment mode in the field. Such as incineration, landfill, etc.
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-containing distillation bottoms used in examples 1 to 8 and comparative example 1 were those produced in the production of polyolefin catalysts according to the following steps: 4.03g of magnesium dichloride, 50mL of toluene, 4.0mL of epichlorohydrin, 4mL of tributyl phosphate and 6.4mL of ethanol are sequentially added into a reactor fully replaced by high-purity nitrogen, the temperature is raised to 70 ℃ under stirring, and the reaction is carried out for 1 hour at the temperature of 70 ℃ after the solid is completely dissolved to form a uniform solution. The system was cooled to-5 ℃ and 40mL of titanium tetrachloride was slowly added dropwise, followed by 3mL of tetraethoxysilane and reacted for 1 hour. The temperature was slowly raised to 80 ℃ and the reaction was carried out for 2 hours. Stopping stirring, standing, quickly layering the suspension, removing supernatant, washing with toluene twice, washing with hexane four times, and blowing with high-purity nitrogen to obtain the solid catalyst 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 hydrocarbon solvent, titanium tetrachloride, high-boiling residue and the like is distilled to remove partial titanium tetrachloride to obtain titanium-containing distillation raffinate, wherein the chlorine content is 60-70wt%.
The titanium-containing distillation bottoms used in examples 9-16 were bottoms produced during the preparation of polyolefin catalysts according to the following procedure: 4.03g of magnesium dichloride, 50mL of toluene, 4.0mL of epichlorohydrin, 4mL of tributyl phosphate and 6.4mL of ethanol are sequentially added into a reactor fully replaced by high-purity nitrogen, the temperature is raised to 70 ℃ under stirring, and the reaction is carried out for 1 hour at the temperature of 70 ℃ after the solid is completely dissolved to form a uniform solution. The system was cooled to-5 ℃ and 40mL of titanium tetrachloride was slowly added dropwise, followed by 3mL of silicon tetrachloride and the reaction was carried out for 1 hour. The temperature was slowly raised to 80 ℃ and the reaction was carried out for 2 hours. Stopping stirring, standing, quickly layering the suspension, removing supernatant, washing with toluene twice, washing with hexane four times, and blowing with high-purity nitrogen to obtain the solid catalyst 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 hydrocarbon solvent, titanium tetrachloride, high-boiling residue and the like is distilled to remove part of titanium tetrachloride to obtain titanium-containing distillation raffinate, wherein the chlorine content is 60-70wt%.
The method for testing the chlorine content in the sample is X-ray fluorescence spectrometry.
Example 1
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 60mL of methanol under the stirring condition, reacting at room temperature for 2h, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) filtering and separating the alcoholysis product to obtain an organic waste liquid with chlorine content of 51.1wt% and a small amount of solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 2
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 60mL of ethanol under the stirring condition, reacting for 2h at 78 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) filtering and separating the alcoholysis product to obtain an organic waste liquid with the chlorine content of 20.5wt% and a small amount of solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 3
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 120mL of methanol under the stirring condition, reacting at room temperature for 2h, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) filtering and separating the alcoholysis product to obtain an organic waste liquid with the chlorine content of 28.2wt% and a small amount of solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 4
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 120mL of ethanol under the stirring condition, reacting for 2h at 78 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) filtering and separating the alcoholysis product to obtain an organic waste liquid with the chlorine content of 23.8wt% and a small amount of solid waste residue. And carrying out incineration treatment on the organic waste liquid, and carrying out landfill treatment on the solid waste residues.
Example 5
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 60mL of ethanol under the stirring condition, reacting for 2h at 78 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) carrying out neutralization reaction on the alcoholysis product and sodium hydroxide solid, reacting at 78 ℃ until the solution is neutral, and carrying out filter-pressing separation on the neutralized solution to obtain organic waste liquid with the chlorine content of 0.3wt% and white solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 6
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 120mL of ethanol while stirring, reacting for 2h at 78 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing to obtain a light yellow alcoholysis product after the reaction is finished. And (3) carrying out neutralization reaction on the alcoholysis product and a sodium hydroxide solid, reacting at 78 ℃ until the solution is neutral, and carrying out filter pressing separation on the neutralized solution to obtain an organic waste liquid with the chlorine content of 0.2wt% and white solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 7
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 60mL of ethylene glycol under the stirring condition, reacting for 2h at 100 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) carrying out neutralization reaction on the alcoholysis product and sodium hydroxide solid, reacting at 100 ℃ until the solution is neutral, and carrying out filter-pressing separation on the neutralized solution to obtain organic waste liquid with the chlorine content of 0.4wt% and white solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 8
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 120mL of ethylene glycol while stirring, reacting for 2 hours at 100 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) carrying out neutralization reaction on the alcoholysis product and sodium hydroxide solid, reacting at 100 ℃ until the solution is neutral, and carrying out filter-pressing separation on the neutralized solution to obtain organic waste liquid with the chlorine content of 0.2wt% and white solid waste residue. And carrying out incineration treatment on the organic waste liquid, and carrying out landfill treatment on the solid waste residues.
Example 9
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 60mL of methanol under the stirring condition, reacting at room temperature for 2h, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And filtering and separating the alcoholysis product to obtain an organic waste liquid with chlorine content of 38.2wt% and a small amount of solid waste residue. And carrying out incineration treatment on the organic waste liquid, and carrying out landfill treatment on the solid waste residues.
Example 10
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 60mL of ethanol under the stirring condition, reacting for 2 hours at 78 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) filtering and separating the alcoholysis product to obtain an organic waste liquid with the chlorine content of 17.1wt% and a small amount of solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 11
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 120mL of methanol under the stirring condition, reacting at room temperature for 2h, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) filtering and separating the alcoholysis product to obtain an organic waste liquid with chlorine content of 22.0wt% and a small amount of solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 12
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 120mL of ethanol under the stirring condition, reacting for 2 hours at 78 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) filtering and separating the alcoholysis product to obtain an organic waste liquid with the chlorine content of 21.3wt% and a small amount of solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 13
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 60mL of ethanol under the stirring condition, reacting for 2h at 78 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) carrying out neutralization reaction on the alcoholysis product and sodium hydroxide solid, reacting at 78 ℃ until the solution is neutral, and carrying out filter-pressing separation on the neutralized solution to obtain organic waste liquid with the chlorine content of 0.5wt% and white solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 14
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 120mL of ethanol while stirring, reacting for 2 hours at 78 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) carrying out neutralization reaction on the alcoholysis product and a sodium hydroxide solid, reacting at 78 ℃ until the solution is neutral, and carrying out filter pressing separation on the neutralized solution to obtain an organic waste liquid with the chlorine content of 0.3wt% and white solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 15
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 60mL of ethylene glycol under the stirring condition, reacting for 2h at 100 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) carrying out neutralization reaction on the alcoholysis product and sodium hydroxide solid, reacting at 100 ℃ until the solution is neutral, and carrying out filter-pressing separation on the neutralized solution to obtain organic waste liquid with the chlorine content of 0.3wt% and white solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Example 16
Adding 30mL of titanium-containing distillation residual liquid into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 120mL of ethylene glycol while stirring, reacting for 2h at 100 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished. And (3) carrying out neutralization reaction on the alcoholysis product and sodium hydroxide solid, reacting at 100 ℃ until the solution is neutral, and carrying out filter-pressing separation on the neutralized solution to obtain organic waste liquid with the chlorine content of 0.2wt% and white solid waste residue. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
Comparative example 1
Adding 60mL of water into a 300mL glass reaction kettle with mechanical stirring, a reflux condenser tube and nitrogen protection, gradually adding 30mL of titanium-containing distillation residual liquid while 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 area, and needs to be transported to a remote area, so that the subsequent processing flow is complex, the cost is high, and the environmental protection is not facilitated.
As can be seen from the comparison between the examples and the comparative examples, compared with the currently adopted method, the method provided by the invention is simpler and more practical, the treatment process of the titanium-containing waste liquid is obviously shortened, the waste water and the waste residues generated in the treatment process are greatly reduced, the chlorine content in the obtained organic waste liquid is greatly reduced, the organic waste liquid can be directly incinerated, and the method has obvious environmental protection and economic benefits. 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 (14)
1. A method for treating a titanium-containing distillation residue, which is produced in the preparation process of a titanium-containing polyolefin catalyst, is characterized by comprising the following steps:
(1) Mixing the titanium-containing distillation residual liquid with an alcohol compound for alcoholysis reaction to obtain an alcoholysis product containing hydrogen chloride;
(2) Directly carrying out solid-liquid separation on the alcoholysis product obtained in the step (1), or carrying out neutralization reaction on the alcoholysis product and an alkaline substance, and then carrying out solid-liquid separation to obtain an organic waste liquid and solid waste residue;
in the step (1), the volume ratio of the alcohol compound to the titanium-containing distillation residual liquid is 0.05-15: 1;
wherein the titanium-containing distillation raffinate is raffinate containing titanium tetrachloride and high-boiling residues, which is obtained by distilling a catalyst mother liquor generated in the preparation process of the titanium polyolefin catalyst to remove part of titanium tetrachloride.
2. The process for treating a titanium-containing distillation residue according to claim 1, wherein said alcohol compound is at least one of a monohydric alcohol, a dihydric alcohol and a polyhydric alcohol.
3. The method for treating titanium-containing distillation residue according to claim 2, wherein the monohydric alcohol is at least one of alcohol compounds represented by the general formula ROH, wherein R is C 1 -C 12 Linear or branched alkyl of (2), C 3 -C 12 Cycloalkyl or C 7 -C 12 Aralkyl group of (1);
the dihydric alcohol is C 2 -C 12 The dihydric alcohol of (1);
the polyol is C 2 -C 12 The trihydric alcohol of (1).
4. The process for treating a titanium-containing distillation residue according to claim 3, wherein the monohydric alcohol is at least one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonanol, n-decanol, cyclopentanol, benzyl alcohol and phenethyl alcohol.
5. The process for treating a titanium-containing distillation residue according to claim 3, wherein said glycol is ethylene glycol and/or propylene glycol.
6. The process for treating a titanium-containing distillation residue according to claim 3, wherein said polyhydric alcohol is glycerin.
7. The process according to claim 1, wherein the volume ratio of the alcohol compound to the titanium-containing distillation residue in the step (1) is from 0.1 to 10:1.
8. the process for treating a titanium-containing distillation residue according to claim 7, wherein the volume ratio of the alcohol compound to the titanium-containing distillation residue is from 0.2 to 5:1.
9. the process for the treatment of titanium-containing distillation residue as claimed in claim 1, wherein in step (1), the alcoholysis reaction is carried out under stirring conditions, and the temperature of the alcoholysis reaction is not higher than the boiling point of the alcohol compound.
10. The process according to claim 1, wherein the titanium-containing distillation residue is mixed with the alcohol compound in the step (1) in such a manner that: adding the alcohol compound into the titanium-containing distillation residual liquid or adding the titanium-containing distillation residual liquid into the alcohol compound.
11. The process according to claim 10, wherein the step (1) of mixing the titanium-containing distillation residue with the alcohol compound is carried out by: adding alcohol compound into the titanium-containing distillation residual liquid.
12. The process for treating a titanium-containing distillation residue according to claim 1, wherein in the step (2), the basic substance is a hydroxide and/or an oxide of an alkali metal and/or an alkaline earth metal.
13. The process for treating a titanium-containing distillation residue according to claim 12, wherein said basic substance is at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide and calcium oxide.
14. The process for treating titanium-containing distillation residue according to any one of claims 1 to 13, wherein the organic waste liquid is directly subjected to incineration treatment, and the solid waste is treated as solid waste.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911015057.8A CN112707530B (en) | 2019-10-24 | 2019-10-24 | Treatment method of titanium-containing distillation residual liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911015057.8A CN112707530B (en) | 2019-10-24 | 2019-10-24 | Treatment method of titanium-containing distillation residual liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112707530A CN112707530A (en) | 2021-04-27 |
| CN112707530B true CN112707530B (en) | 2023-04-07 |
Family
ID=75540240
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911015057.8A Active CN112707530B (en) | 2019-10-24 | 2019-10-24 | Treatment method of titanium-containing distillation residual liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112707530B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2962488A (en) * | 1955-12-27 | 1960-11-29 | Goodrich Gulf Chemical Inc | Removal of catalyst from olefin polymer by treatment with alcohol under inert atmosphere |
| CN1440426A (en) * | 2000-07-11 | 2003-09-03 | 联合碳化化学及塑料技术公司 | Method of reducing formation of precipitates in solvent recovery system |
Family Cites Families (7)
| 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 |
| CN1078565C (en) * | 1999-01-22 | 2002-01-30 | 清华大学 | Method for preparing nano sized titanium dioxide powder by alcoholysis from titanic chloride |
| JP4072995B2 (en) * | 2000-12-01 | 2008-04-09 | 三井化学株式会社 | Method for recovering titanium compound and method for producing titanium halide |
| CN1403464A (en) * | 2002-10-15 | 2003-03-19 | 上海交通大学 | Prepn of dibasic alkoxide of titanium |
| EP2452920A1 (en) * | 2010-11-12 | 2012-05-16 | Borealis AG | A method for recovering transition metal tetrahalide and hydrocarbons from a waste stream |
| CN106277046B (en) * | 2015-06-24 | 2018-01-02 | 中国石油化工股份有限公司 | A kind of processing method of the waste liquid containing titanium tetrachloride |
| US20190184306A1 (en) * | 2016-08-03 | 2019-06-20 | Clariant International Ltd | Method for recovering titanium (halo) alkoxide from a waste liquid |
-
2019
- 2019-10-24 CN CN201911015057.8A patent/CN112707530B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2962488A (en) * | 1955-12-27 | 1960-11-29 | Goodrich Gulf Chemical Inc | Removal of catalyst from olefin polymer by treatment with alcohol under inert atmosphere |
| CN1440426A (en) * | 2000-07-11 | 2003-09-03 | 联合碳化化学及塑料技术公司 | Method of reducing formation of precipitates in solvent recovery system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112707530A (en) | 2021-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105189357A (en) | Methods for purifying aluminium ions | |
| JP2013503920A (en) | Systems and processes for biodiesel production | |
| CN103030232A (en) | Method for treating titanium-containing waste liquid produced by polyolefin catalyst | |
| WO2013110723A1 (en) | Process for preparing ethylene and other olefins from aqueous solutions of the corresponding alcohols | |
| CN112707560B (en) | Treatment method of titanium-containing waste liquid, titanium dioxide raw material and application | |
| CN105452230B (en) | For manufacturing the method for epoxy monomer and epoxides | |
| CN112707530B (en) | Treatment method of titanium-containing distillation residual liquid | |
| CN112707559B (en) | Treatment method of titanium-containing distillation raffinate | |
| CN104768878B (en) | The method for handling the waste water containing fluorine component | |
| CN112707532B (en) | Treatment method of titanium-containing distillation residual liquid, titanium white raw material and application | |
| CN105384629B (en) | A kind of energy-conserving and environment-protective production technology of the different monooctyl ester of lactic acid | |
| CN112707437A (en) | Treatment method of titanium tetrachloride-containing waste liquid | |
| CN112707435A (en) | Method for recovering refined titanium tetrachloride from titanium tetrachloride-containing waste liquid | |
| CN112707561B (en) | Treatment method of titanium-containing waste liquid | |
| CN102627561B (en) | Preparation process for plasticizer-tributyl citrate | |
| CN102992415B (en) | Treatment method of polyolefin catalyst residual liquid | |
| CN112707449B (en) | Method for treating titanium-containing waste liquid | |
| CN112707557B (en) | Treatment method of titanium-containing waste liquid | |
| CN114426306B (en) | Titanium polyolefin catalyst mother liquor treatment device and method | |
| CN112707556A (en) | Titanium-containing waste liquid treatment method and titanium-containing dry powder | |
| CN112708782B (en) | Titanium-containing waste liquid treatment method and titanium-containing dry powder | |
| CN112723580A (en) | Method for reducing chlorine content in chlorine-containing organic waste liquid and method for treating chlorine-containing organic waste liquid | |
| CN112704894A (en) | Catalyst solvent recovery method and titanium-containing solid | |
| CN1067049C (en) | Process for producing terephthalic acid | |
| CN112707436B (en) | Treatment method of titanium tetrachloride-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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |