CN112898113A - Method for recycling polyolefin catalyst waste liquid - Google Patents
Method for recycling polyolefin catalyst waste liquid Download PDFInfo
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- CN112898113A CN112898113A CN201911222593.5A CN201911222593A CN112898113A CN 112898113 A CN112898113 A CN 112898113A CN 201911222593 A CN201911222593 A CN 201911222593A CN 112898113 A CN112898113 A CN 112898113A
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- waste liquid
- water
- polyolefin catalyst
- catalyst waste
- organic
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- 239000007788 liquid Substances 0.000 title claims abstract description 49
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004064 recycling Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000010936 titanium Substances 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012074 organic phase Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000010410 layer Substances 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 239000012188 paraffin wax Substances 0.000 claims description 5
- 239000012071 phase Substances 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002407 reforming Methods 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 14
- 238000011084 recovery Methods 0.000 abstract description 13
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 150000003609 titanium compounds Chemical class 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 16
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- -1 alkoxy titanium Chemical compound 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G7/00—Distillation of hydrocarbon oils
- C10G7/006—Distillation of hydrocarbon oils of waste oils other than lubricating oils, e.g. PCB's containing oils
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The invention discloses a method for recycling polyolefin catalyst waste liquid. The method comprises the following steps: mixing the polyolefin catalyst waste liquid with water, standing for layering, and respectively recovering titanium and an organic oil layer in a water layer. By applying the technical scheme of the invention, organic matters and inorganic matters in the polyolefin catalyst waste liquid are respectively recovered, so that the discharge of the waste liquid is reduced, most of titanium compounds and organic phase substances are also recovered, and after the recovery treatment, no toxic and harmful substances are discharged.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for recycling polyolefin catalyst waste liquid.
Background
In the industrial production of polyolefins, Ziegler-Natta catalysts are used in a large amount, and a large amount of titanium tetrachloride, hexane, paraffin, etc. are used in the preparation process. After the polyolefin catalyst is separated, more titanium-containing waste liquid is generated, the components of the waste liquid are complex, the waste liquid mainly contains unreacted carbon tetrachloride and some organic solvents, the waste liquid cannot directly enter a sewage and sump oil treatment unit for treatment, and the components can be further recycled.
Some patent technologies adopt distillation to separate, for example, CN103420437B, an organic solvent is added into titanium-containing waste liquid, after mixing thoroughly, distillation is carried out in a distillation apparatus, titanium tetrachloride is separated from the top of the distillation apparatus, and an alkali solution is added into the remaining mixed solution in the distillation apparatus to carry out hydrolysis treatment, and then the organic solvent is recovered. Titanium tetrachloride has a boiling point of 136.4 c and the process is not applicable when the organic solvent used has a wide boiling range, covering the boiling point range of titanium tetrachloride.
CN101717113A invented a method for separating titanium tetrachloride and alkoxy titanium by low-temperature cold-separation crystallization, but this method needs to reduce the temperature of the system to below 0 to-25 deg.C, and the treatment consumes a long time, and because of the need of providing a large amount of cold energy, the energy consumption is large.
CN101065506A invented a method for continuously recovering titanium tetrachloride from titanium-containing waste liquid, which uses a thin film evaporator to form a flowing liquid film for evaporation to recover titanium tetrachloride, but this method has high requirements for equipment and requires a large investment in equipment.
Disclosure of Invention
The invention aims to provide a method for recycling polyolefin catalyst waste liquid, and provides a method for recycling polyolefin catalyst waste liquid, which is simple to operate, low in investment and quick in return.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method of recycling a polyolefin catalyst waste liquid. The method comprises the following steps: mixing the polyolefin catalyst waste liquid with water, standing for layering, and respectively recovering titanium and an organic oil layer in a water layer.
Further, the polyolefin catalyst waste liquid is mixed with water at normal temperature; preferably, the water is deionized water.
Further, the volume ratio of the mass of the polyolefin catalyst waste liquid to the water is 1: 0.5-3.
Further, the volume ratio of the mass of the polyolefin catalyst waste liquid to water was 1: 1.
Further, the recovery of the organic oil layer comprises: the organic phase and the inorganic phase are separated to obtain an organic oil layer, hexane and toluene are recovered from the organic oil layer by means of distillation or rectification, and the rest of the component rich in paraffin or naphthene is used as a reforming material or a cracking material.
Further, recovering titanium in the aqueous layer comprises: and adding alkali to adjust the pH value of the water layer to 7-14, separating out a white solid, performing solid-liquid separation in a suction filtration mode, and drying at normal pressure to obtain a titanium dioxide solid.
Further, the added alkali is one or more selected from the group consisting of sodium hydroxide, calcium hydroxide, iron hydroxide and potassium hydroxide.
Further, the added base is sodium hydroxide.
Further, the mass percentage concentration of the added alkali is 1-50%.
Further, the mass percentage concentration of the added alkali is 10-20%.
By applying the technical scheme of the invention, organic matters and inorganic matters in the polyolefin catalyst waste liquid are respectively recovered, so that the discharge of the waste liquid is reduced, most of titanium compounds and organic phase substances are also recovered, and after the recovery treatment, no toxic and harmful substances are discharged.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
Aiming at the problem that a large amount of waste liquid containing titanium, alkane and other organic matters is generated in the production and preparation process of the polyolefin catalyst, the invention establishes a method for separating, recycling and utilizing, thereby reducing pollution and increasing benefit.
According to an exemplary embodiment of the present invention, a method for recycling polyolefin catalyst waste is provided. The method comprises the following steps: mixing the polyolefin catalyst waste liquid with water, standing for layering, and respectively recovering titanium and an organic oil layer in a water layer. By applying the technical scheme of the invention, organic matters and inorganic matters in the polyolefin catalyst waste liquid are respectively recovered, so that the discharge of the waste liquid is reduced, most of titanium compounds and organic phase substances are also recovered, and after the recovery treatment, no toxic and harmful substances are discharged.
In a typical embodiment of the present invention, the polyolefin catalyst waste liquid is mixed with water at normal temperature, so that the operation is convenient, and the investment on equipment and consumables is not excessive. Preferably, the water is deionized water. Preferably, the volume ratio (g/mL) of the mass of the polyolefin catalyst waste liquid to the volume of water is 1: 0.5-3, and in the ratio, inorganic substances, particularly titanium in the polyolefin catalyst waste liquid can be sufficiently separated into a water phase, and the burden of subsequent waste liquid treatment and titanium recovery is not increased; more preferably, the volume ratio of the mass of the polyolefin catalyst waste liquid to the water is 1: 1.
According to an exemplary embodiment of the present invention, the recovering of the organic oil layer comprises: the organic phase and the inorganic phase are separated to obtain an organic oil layer, hexane and toluene are recovered from the organic oil layer by adopting a distillation or rectification mode, and the rest components rich in paraffin or naphthene are used as a reforming body or a cracking material, so that the organic matters in the polyolefin catalyst waste liquid can be fully recovered and utilized.
According to a typical embodiment of the invention, the step of recovering titanium in the water layer comprises the steps of adding alkali to adjust the pH value of the water layer to 7-14, separating out white solids, performing solid-liquid separation in a suction filtration mode, and drying at normal pressure to obtain titanium dioxide solids. Wherein, the added alkali is one or more selected from the group consisting of sodium hydroxide, calcium hydroxide, ferric hydroxide and potassium hydroxide, and sodium hydroxide is preferred because of its strong alkalinity, low price and easy purchase. In addition, in order to improve the working efficiency and reduce the cost, the mass percentage concentration of the added alkali is 1 to 50 percent, and more preferably 10 to 20 percent.
In a specific embodiment of the invention, the method comprises the steps of mixing the polyolefin catalyst waste liquid with the mass-to-volume ratio of 1: 0.5-3 with deionized water at normal temperature, slowly adding the polyolefin waste liquid into the deionized water and continuously and rapidly stirring, standing and separating in a separating funnel after complete reaction, and respectively taking an upper oil layer and a lower water layer. And further distilling and cutting the oil layer to obtain organic matters with different distillation ranges. Wherein the hexane and toluene content in the fraction at the temperature of less than 100 ℃ is higher, the hexane and toluene with higher content are further separated and used respectively, and the fraction at the temperature of more than 100 ℃ is mainly paraffin and naphthene which can be used as cracking material or reforming material. The water layer is acidic, white precipitate is generated after the water layer is neutralized by adding alkali liquor, and the titanium dioxide solid is obtained after the water layer is dried under normal pressure after the water layer is filtered. By applying the technical scheme of the invention, the titanium dioxide is obtained by hydrolysis separation, distillation recovery of organic solution, acid-base neutralization and drying, the recovery rate is high, no toxic and harmful substance is discharged, and the method is green and environment-friendly.
The following examples are provided to further illustrate the advantageous effects of the present invention.
Example 1
And slowly pouring 500g of polyolefin catalyst waste liquid into 500mL of normal-temperature deionized water, quickly stirring by using a glass rod, and pouring into a separating funnel for standing and separation when the reaction is complete and no insoluble substances exist. 260g of an upper organic layer was obtained. The organics were cut by distillation, fractions collected and recovery as shown in table 1 below:
table 1: distillation recovery of organic layer components
500ml of the lower aqueous layer of example 1 was taken, and 20% sodium hydroxide was slowly added thereto with continuous stirring to give a large amount of a white solid. And (3) testing the pH value of the solution, stopping adding the alkali liquor when the pH value is more than 7, standing for 2 hours, precipitating a white solid to the lower layer of the container, pouring out the upper water layer, and filtering the lower titanium dioxide suspension. The filter cake was dried at atmospheric pressure for 12h to give 450.92g of titanium dioxide solid.
Example 2
425g of polyolefin catalyst waste liquid is slowly poured into 1000ml of normal-temperature deionized water, the mixture is rapidly stirred by a glass rod, and when the reaction is complete and no insoluble substances exist, the mixture is poured into a separating funnel for standing and separation. 226g of the upper organic layer was obtained. The organics were cut by distillation, fractions collected and recovery as shown in table 2 below:
table 2: distillation recovery of organic layer components
1000ml of the lower aqueous layer of example 2 was taken and 20% sodium hydroxide was slowly added with constant stirring to give a large amount of white solid. And (3) testing the pH value of the solution, stopping adding the alkali liquor when the pH value is more than 7, standing for 2 hours, precipitating a white solid to the lower layer of the container, pouring out the upper water layer, and filtering the lower titanium dioxide suspension. The filter cake was dried at atmospheric pressure for 12h to give 228.65g of titanium dioxide solid.
Example 3
400g of polyolefin catalyst waste liquid is slowly poured into 300ml of normal temperature deionized water, the mixture is continuously and rapidly stirred by a glass rod, and after the solution reacts for a period of time, the upper layer solution and the lower layer solution are separated. However, the upper solution had reddish brown suspended matter, which dissolved slowly, and dissolved slowly after vigorously stirring for ten minutes. After dissolution, the solution is divided into an organic phase and an aqueous phase.
Example 4
200g of polyolefin catalyst waste liquid is slowly poured into 100ml of normal temperature deionized water, the mixture is continuously and rapidly stirred by a glass rod, and after the solution reacts for a period of time, the upper layer solution and the lower layer solution are separated. However, the upper solution has more reddish brown suspended matters which are slowly dissolved, the upper solution still exists after being vigorously stirred for ten minutes, and most suspended matters can be dissolved after the stirring is continued for thirty minutes. After dissolution, the solution is divided into an organic phase and an aqueous phase. It can be seen that if too little water is added, the reaction rate is slowed down and the reaction time is prolonged.
Example 5
100g of polyolefin catalyst waste liquid is slowly poured into 300ml of normal-temperature deionized water, the mixture is quickly stirred by a glass rod, the separated reddish brown solid can be seen to be quickly dissolved, the reaction is quick, when the reaction is complete and no insoluble substances exist, the clear boundary between the organic matter and the water phase can be seen, and the separation can be realized through a separating funnel.
The more water is added in the reaction, the reaction speed can be accelerated, insoluble substances are dissolved out better, but the organic matters in the waste liquid are fixed, more organic matters can not be recycled due to the increase of water quantity, and the waste or the workload of the next separation is increased due to the excessive water quantity.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the method respectively treats and recovers the titanium tetrachloride and the organic layer solution after hydrolysis, has no emission of toxic and harmful substances after recovery treatment, and has high recovery rate and good treatment effect.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for recycling polyolefin catalyst waste liquid is characterized by comprising the following steps: mixing the polyolefin catalyst waste liquid with water, standing for layering, and respectively recovering titanium and an organic oil layer in a water layer.
2. The method according to claim 1, wherein the polyolefin catalyst waste liquid is mixed with water at normal temperature; preferably, the water is deionized water.
3. The method according to claim 1, wherein the volume ratio of the mass of the polyolefin catalyst waste liquid to the water is 1: 0.5-3.
4. The method of claim 3, wherein the volume ratio of the mass of the polyolefin catalyst waste liquid to the water is 1: 1.
5. The method of claim 1, wherein the recovering of the organic oil layer comprises: the organic phase and the inorganic phase are separated to obtain an organic oil layer, hexane and toluene are recovered from the organic oil layer by means of distillation or rectification, and the rest of the component rich in paraffin or naphthene is used as a reforming material or a cracking material.
6. The method of claim 1, wherein the recovering titanium in the aqueous layer comprises: and adding alkali to adjust the pH value of the water layer to 7-14, separating out a white solid, performing solid-liquid separation in a suction filtration mode, and drying at normal pressure to obtain a titanium dioxide solid.
7. The method according to claim 6, wherein the alkali added is one or more selected from the group consisting of sodium hydroxide, calcium hydroxide, iron hydroxide and potassium hydroxide.
8. The method of claim 7, wherein the base added is sodium hydroxide.
9. The method according to claim 6, wherein the alkali is added in a concentration of 1 to 50% by mass.
10. The method according to claim 9, wherein the alkali is added in a concentration of 10 to 20% by mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201911222593.5A CN112898113A (en) | 2019-12-03 | 2019-12-03 | Method for recycling polyolefin catalyst waste liquid |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911222593.5A CN112898113A (en) | 2019-12-03 | 2019-12-03 | Method for recycling polyolefin catalyst waste liquid |
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| CN112898113A true CN112898113A (en) | 2021-06-04 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041981A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for treating polyolefin catalyst tower bottom liquid extraction precipitate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3493628A (en) * | 1967-08-17 | 1970-02-03 | Marathon Oil Co | Recovery and recycle of ticl4 in processes for the reaction of haloethers with olefins |
| US4914257A (en) * | 1988-05-23 | 1990-04-03 | Amoco Corporation | Method and apparatus for recovering high purity toluene, hexane, titanium tetrachloride and tetrahydrofuran from mixtures |
| CN104445701A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Method for processing titanium-containing organic matter-containing waste acid water from polyolefin catalyst |
| CN106277046A (en) * | 2015-06-24 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of processing method containing titanium tetrachloride waste liquid |
-
2019
- 2019-12-03 CN CN201911222593.5A patent/CN112898113A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3493628A (en) * | 1967-08-17 | 1970-02-03 | Marathon Oil Co | Recovery and recycle of ticl4 in processes for the reaction of haloethers with olefins |
| US4914257A (en) * | 1988-05-23 | 1990-04-03 | Amoco Corporation | Method and apparatus for recovering high purity toluene, hexane, titanium tetrachloride and tetrahydrofuran from mixtures |
| CN104445701A (en) * | 2013-09-16 | 2015-03-25 | 中国石油化工股份有限公司 | Method for processing titanium-containing organic matter-containing waste acid water from polyolefin catalyst |
| CN106277046A (en) * | 2015-06-24 | 2017-01-04 | 中国石油化工股份有限公司 | A kind of processing method containing titanium tetrachloride waste liquid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041981A (en) * | 2021-10-28 | 2023-05-02 | 中国石油化工股份有限公司 | Method for treating polyolefin catalyst tower bottom liquid extraction precipitate |
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