CN112707559A - Treatment method of titanium-containing distillation residual liquid - Google Patents

Treatment method of titanium-containing distillation residual liquid Download PDF

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Publication number
CN112707559A
CN112707559A CN201911024224.5A CN201911024224A CN112707559A CN 112707559 A CN112707559 A CN 112707559A CN 201911024224 A CN201911024224 A CN 201911024224A CN 112707559 A CN112707559 A CN 112707559A
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titanium
distillation
alcohol
treatment
alcoholysis
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CN112707559B (en
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贾凡
王毅
郭子芳
苟清强
马冬
李颖
黄庭
杨红旭
曹昌文
俸艳芸
安京燕
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/008—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals for liquid waste
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • 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
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/06—Flash evaporation
    • 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
    • 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
    • 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

Abstract

The invention belongs to the field of industrial waste liquid treatment, and relates to a treatment method of titanium-containing distillation raffinate. 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) distilling the alcoholysis product obtained in the step (1) to remove hydrogen chloride in the alcoholysis product to obtain the alcoholysis product with reduced chlorine content; (3) and (3) directly carrying out solid-liquid separation on the alcoholysis product with reduced chlorine content obtained in the step (2), or carrying out neutralization reaction on the alcoholysis product with reduced chlorine content 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

Treatment method of titanium-containing distillation residual liquid
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 method for treating titanium-containing waste liquid produced by polyolefin catalyst, comprising the following 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, 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 TiO2/CaCl2·nH2O。
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 process 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) distilling the alcoholysis product obtained in the step (1) to remove hydrogen chloride in the alcoholysis product to obtain the alcoholysis product with reduced chlorine content;
(3) and (3) directly carrying out solid-liquid separation on the alcoholysis product with reduced chlorine content obtained in the step (2), or carrying out neutralization reaction on the alcoholysis product with reduced chlorine content 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. The alcoholysis product is subjected to distillation treatment and is preferably combined with a neutralization reaction with an alkaline substance, so that hydrogen chloride contained in the alcoholysis product can be further 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 more 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 present 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) distilling the alcoholysis product obtained in the step (1) to remove hydrogen chloride in the alcoholysis product to obtain the alcoholysis product with reduced chlorine content;
(3) and (3) directly carrying out solid-liquid separation on the alcoholysis product with reduced chlorine content obtained in the step (2), or carrying out neutralization reaction on the alcoholysis product with reduced chlorine content and an alkaline substance, and then carrying out solid-liquid separation to obtain an organic waste liquid and solid waste residue.
The term "titanium tetrachloride-containing distillation residue liquid" as a treatment object of the present invention, which is a distillation residue liquid 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 liquid containing titanium tetrachloride and high boiling components obtained by distilling a part of titanium tetrachloride in 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 C1-C12Linear or branched alkyl of (2), C3-C12Cycloalkyl or C7-C12Aralkyl 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 C2-C12The dihydric alcohol of (1); further preferred is ethylene glycol and/or propylene glycol.
Specifically, the polyol is preferably C2-C12The trihydric alcohol of (1); further preferred is glycerin.
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. The HCl gas produced during the alcoholysis reaction may be neutralized and absorbed using conventional methods, for example, by absorbing the HCl gas produced 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, in the step (2), the distillation treatment may be an atmospheric distillation treatment or a vacuum distillation treatment, and the number of times of distillation may be one or more. The distillation treatment employed in the present invention is intended to remove hydrogen chloride therefrom, and for this purpose, the skilled person will be able to select suitable distillation treatment conditions, including: the temperature of the distillation treatment is not lower than the initial boiling point of the alcoholysis product, and the time of the distillation treatment is that the distillation is carried out until part or all of the alcohol compounds in the alcoholysis product are distilled off.
According to the present invention, preferably, in the specific distillation process, the step (2) further comprises: after the distillation treatment, the alcohol compound and/or the distillation fraction is added to the product obtained by distillation to obtain an alcoholysis product with reduced chlorine content. The distillation fraction can be recycled.
According to the present invention, the distillation treatment is preferably carried out until substantially all of the alcohol compound in the alcoholysis product is distilled off, and then the alcohol compound and/or the distillation fraction is added to the resultant product of the distillation, and this is repeated several times, whereby the chlorine content in the alcoholysis product can be reduced. After the last distillation treatment, the alcohol compound and/or the distillation fraction are preferably added to enhance the fluidity of the alcoholysate and facilitate subsequent solid-liquid separation. The volume of the alcohol compound and/or the distillate added each time is preferably such that the total volume of the system after addition is equivalent to the total volume of the system after the first addition of the alcohol compound. Therefore, in the case of distilling substantially all of the alcohol compound each time, the volume of the alcohol compound newly added and/or the distilled fraction is the same as the volume of the alcohol compound first added.
According to the method of the present invention, the basic substance is added in step (3) in order to neutralize hydrogen chloride in the alcoholysis solution, and thus, 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 with reduced chlorine content can be directly subjected to incineration treatment, and the incineration treatment is carried out by adopting a conventional treatment mode meeting the environmental protection regulations. The solid waste residue 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, pumping out supernatant, washing twice with toluene and four times with hexane, 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 60-70 wt%.
The titanium-containing distillation bottoms used in examples 9-16 were those 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, pumping out supernatant, washing twice with toluene and four times with hexane, 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 60-70 wt%.
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 100mL of methanol under the stirring condition, reacting for 2h at 64 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished, wherein the chlorine content is 30.5 wt%. And (3) distilling the alcoholysis product for 1 time under normal pressure at the distillation temperature of 64 ℃ until all methanol is distilled out basically, re-dissolving the alcoholysis product by using 100mL of methanol after the distillation is finished, and then filtering and separating to obtain an organic waste liquid with the chlorine content of 15.3 wt% 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 120mL of methanol under the stirring condition, reacting for 2h at 64 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished, wherein the chlorine content is 27.6 wt%. And (3) repeatedly carrying out 2 times of atmospheric distillation on the alcoholysis product, wherein the distillation temperature is 64 ℃, each time of distillation is carried out until all methanol is distilled out basically, and the alcoholysis product is dissolved again by 120mL of methanol after each time of distillation. Then filtering and separating to obtain organic waste liquid with the chlorine content of 11.5 wt% 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 100mL of methanol under the stirring condition, reacting for 2h at 64 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished, wherein the chlorine content is 30.5 wt%. And (3) carrying out 1 atmospheric distillation on the alcoholysis product at the distillation temperature of 64 ℃ until the methanol is basically distilled out, and re-dissolving the alcoholysis product by using 100mL of methanol after the distillation is finished to obtain a liquid mixture with the chlorine content of 15.3 wt%. And (3) carrying out neutralization reaction on the liquid mixture and sodium hydroxide solid, reacting at 64 ℃ until the solution is neutral, and then carrying out filter pressing separation to obtain organic waste liquid and white solid waste residue with the chlorine content of 0.4 wt%. 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 methanol under the stirring condition, reacting for 2h at 64 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished, wherein the chlorine content is 27.6 wt%. And (3) repeatedly carrying out 2 times of atmospheric distillation on the alcoholysis product, wherein the distillation temperature is 64 ℃, each time of distillation is till the methanol is basically distilled out, and after each time of distillation is finished, 120mL of methanol is used for redissolving to obtain a liquid mixture with the chlorine content of 11.5 wt%. And (3) carrying out neutralization reaction on the liquid mixture and sodium hydroxide solid, reacting at 64 ℃ until the solution is neutral, and then carrying out filter pressing separation to obtain organic waste liquid and white solid waste residue with the chlorine content of 0.2 wt%. And the organic waste liquid is subjected to incineration treatment, and the solid waste residue is subjected to landfill treatment.
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 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, wherein the chlorine content is 23.8 wt%. And (3) distilling the alcoholysis product for 1 time at normal pressure at the distillation temperature of 78 ℃ until all ethanol is distilled out, re-dissolving the alcoholysis product with 120mL of ethanol after the distillation is finished, and then filtering and separating to obtain an organic waste liquid with the chlorine content of 10.1 wt% 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 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 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, wherein the chlorine content is 23.8 wt%. And (3) repeatedly carrying out 2 times of atmospheric distillation on the alcoholysis product, wherein the distillation temperature is 78 ℃, each time of distillation is carried out until all ethanol is distilled out basically, and the alcoholysis product is re-dissolved by 120mL of ethanol after each time of distillation is finished. Then filtering and separating to obtain organic waste liquid with chlorine content of 8.4 wt% 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 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 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, wherein the chlorine content is 23.8 wt%. And (3) carrying out 1-time atmospheric distillation on the alcoholysis product at the distillation temperature of 78 ℃ until all ethanol is distilled out, and re-dissolving the alcoholysis product by using 120mL of ethanol after the distillation is finished to obtain a liquid mixture with the chlorine content of 10.1 wt%. And (3) carrying out neutralization reaction on the liquid mixture and sodium hydroxide solid, reacting at 78 ℃ until the solution is neutral, and then carrying out filter pressing separation to obtain organic waste liquid with the chlorine content of 0.5 wt% 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 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, wherein the chlorine content is 23.8 wt%. And (3) repeatedly carrying out 2 times of atmospheric distillation on the alcoholysis product, wherein the distillation temperature is 78 ℃, each time of distillation is carried out until all ethanol is distilled out basically, and after each time of distillation is finished, 120mL of ethanol is used for redissolving to obtain a liquid mixture with the chlorine content of 8.4 wt%. And (3) carrying out neutralization reaction on the liquid mixture and sodium hydroxide solid, reacting at 78 ℃ until the solution is neutral, and then carrying out filter pressing separation to obtain organic waste liquid with the chlorine content of 0.3 wt% 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 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 100mL of methanol under the stirring condition, reacting for 2h at 64 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished, wherein the chlorine content is 27.8 wt%. And (3) distilling the alcoholysis product for 1 time under normal pressure at the distillation temperature of 64 ℃ until all methanol is distilled out basically, re-dissolving the alcoholysis product by using 100mL of methanol after the distillation is finished, and then filtering and separating to obtain an organic waste liquid with the chlorine content of 13.3 wt% 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 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 120mL of methanol under the stirring condition, reacting for 2h at 64 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished, wherein the chlorine content is 25.8 wt%. And (3) repeatedly carrying out 2 times of atmospheric distillation on the alcoholysis product, wherein the distillation temperature is 64 ℃, each time of distillation is carried out until all methanol is distilled out basically, and the alcoholysis product is dissolved again by 120mL of methanol after each time of distillation. Then, the organic waste liquid with the chlorine content of 9.5 wt% and a small amount of solid waste residue are obtained after filtration and separation. 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 100mL of methanol under the stirring condition, reacting for 2h at 64 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished, wherein the chlorine content is 27.8 wt%. And (3) carrying out 1 atmospheric distillation on the alcoholysis product at the distillation temperature of 64 ℃ until the methanol is basically distilled out, and re-dissolving the alcoholysis product by using 100mL of methanol after the distillation is finished to obtain a liquid mixture with the chlorine content of 13.3 wt%. And (3) carrying out neutralization reaction on the liquid mixture and sodium hydroxide solid, reacting at 64 ℃ until the solution is neutral, and then carrying out filter pressing separation to obtain organic waste liquid and white solid waste residue with the chlorine content of 0.5 percent by weight. 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 methanol under the stirring condition, reacting for 2h at 64 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing, and obtaining light yellow alcoholysis product after the reaction is finished, wherein the chlorine content is 25.8 wt%. And (3) repeatedly carrying out 2 times of atmospheric distillation on the alcoholysis product, wherein the distillation temperature is 64 ℃, each time of distillation is till the methanol is basically distilled out, and after each time of distillation is finished, 120mL of methanol is used for redissolving to obtain a liquid mixture with the chlorine content of 9.5 wt%. And (3) carrying out neutralization reaction on the liquid mixture and sodium hydroxide solid, reacting at 64 ℃ until the solution is neutral, and then carrying out filter pressing separation to obtain organic waste liquid and white solid waste residue with the chlorine content of 0.3 wt%. 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 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, wherein the chlorine content is 21.6 wt%. And (3) distilling the alcoholysis product for 1 time under normal pressure at the distillation temperature of 78 ℃ until all ethanol is distilled out, re-dissolving the alcoholysis product with 120mL of ethanol after the distillation is finished, and then filtering and separating to obtain an organic waste liquid with the chlorine content of 9.8 wt% 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 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 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, wherein the chlorine content is 21.6 wt%. And (3) repeatedly carrying out 2 times of atmospheric distillation on the alcoholysis product, wherein the distillation temperature is 78 ℃, each time of distillation is carried out until all ethanol is distilled out basically, and the alcoholysis product is re-dissolved by 120mL of ethanol after each time of distillation is finished. Then, the organic waste liquid with the chlorine content of 7.3 wt% and a small amount of solid waste residue are obtained after filtration and separation. 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 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, wherein the chlorine content is 21.6 wt%. And (3) carrying out 1-time atmospheric distillation on the alcoholysis product at the distillation temperature of 78 ℃ until all ethanol is distilled out, and re-dissolving the alcoholysis product by using 120mL of ethanol after the distillation is finished to obtain a liquid mixture with the chlorine content of 9.8 wt%. And (3) carrying out neutralization reaction on the liquid mixture and sodium hydroxide solid, reacting at 78 ℃ until the solution is neutral, and then carrying out filter pressing separation to obtain organic waste liquid with the chlorine content of 0.3 wt% 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 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, wherein the chlorine content is 21.6 wt%. And (3) repeatedly carrying out 2 times of atmospheric distillation on the alcoholysis product, wherein the distillation temperature is 78 ℃, each time of distillation is carried out until all ethanol is distilled out basically, and after each time of distillation is finished, 120mL of ethanol is used for redissolving to obtain a liquid mixture with the chlorine content of 7.3 wt%. And (3) carrying out neutralization reaction on the liquid mixture and sodium hydroxide solid, reacting at 78 ℃ until the solution is neutral, and then carrying out filter pressing separation to obtain organic waste liquid with the chlorine content of 0.2 wt% 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 under the stirring condition, keeping the reaction temperature below 100 ℃, discharging HCl generated in the reaction process through tail gas, neutralizing and absorbing the HCl, and obtaining an oil, water and solid three-phase mixture after the reaction is finished. Due to the water and HCl, the mixture was acidic and difficult to incinerate. Particularly, under the increasingly strict environmental requirements, the mixture is difficult to be processed in the catalyst production field, and needs to be transported to a remote area, so that the subsequent processing flow is complicated, the cost is high, and the environmental protection is not facilitated.
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 (10)

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) distilling the alcoholysis product obtained in the step (1) to remove hydrogen chloride in the alcoholysis product to obtain the alcoholysis product with reduced chlorine content;
(3) and (3) directly carrying out solid-liquid separation on the alcoholysis product with reduced chlorine content obtained in the step (2), or carrying out neutralization reaction on the alcoholysis product with reduced chlorine content and an alkaline substance, and then carrying out solid-liquid separation to obtain an organic waste liquid and solid waste residue.
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 C1-C12Linear or branched alkyl of (2), C3-C12Cycloalkyl or C7-C12Aralkyl group of (1); the monohydric alcohol is 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 phenethyl alcohol;
the dihydric alcohol is C2-C12The dihydric alcohol of (1); preferably ethylene glycol and/or propylene glycol;
the polyol is C2-C12The trihydric alcohol of (1); glycerol is preferred.
4. The method for treating titanium-containing distillation residue according to claim 1, wherein in the step (1), the volume ratio of the alcohol compound to the titanium-containing distillation residue is 0.05 to 15: 1, preferably 0.1 to 10: 1, more preferably 0.2 to 5: 1.
5. the process for the treatment of titanium-containing distillation residue according to 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;
the method for mixing the titanium-containing distillation raffinate and the alcohol compound comprises the following steps: adding the alcohol compound into the titanium-containing distillation residual liquid or adding the titanium-containing distillation residual liquid into the alcohol compound, preferably adding the alcohol compound into the titanium-containing distillation residual liquid.
6. The process for treating a titanium-containing distillation residue according to claim 1, wherein in the step (2), the distillation treatment is an atmospheric distillation treatment or a vacuum distillation treatment, and the number of times of distillation is one or more; the temperature of the distillation treatment is not lower than the initial boiling point of the alcoholysate.
7. The process for treating a titanium-containing distillation residue according to claim 1, wherein the step (2) further comprises: after the distillation treatment, the alcohol compound and/or the distillation fraction is added to the product obtained by the distillation.
8. The process for treating a titanium-containing distillation residue according to claim 1, wherein in the step (3), the basic substance is selected from hydroxides and/or oxides of alkali metals and/or alkaline earth metals; preferably at least one of sodium hydroxide, potassium hydroxide, calcium hydroxide and calcium oxide.
9. The process for treating a titanium-containing distillation residue as claimed in claim 1, wherein the titanium-containing distillation residue is a residue containing titanium tetrachloride and high boiling components obtained by distilling a part of titanium tetrachloride off from a catalyst mother liquor produced in the production of a titanium-based polyolefin catalyst.
10. The process for treating titanium-containing distillation residue according to any one of claims 1 to 9, wherein the organic waste liquid is directly subjected to incineration treatment, and the solid waste is treated as solid waste.
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