CN1161318A - Method for removal of metal (Ti or V) alkoxide compounds from liquid hydrocarbon - Google Patents
Method for removal of metal (Ti or V) alkoxide compounds from liquid hydrocarbon Download PDFInfo
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- CN1161318A CN1161318A CN 96121938 CN96121938A CN1161318A CN 1161318 A CN1161318 A CN 1161318A CN 96121938 CN96121938 CN 96121938 CN 96121938 A CN96121938 A CN 96121938A CN 1161318 A CN1161318 A CN 1161318A
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Abstract
A method for recovering titanium and vanadium compounds, such as alkoxides, from a liquid hydrocarbon mixture by hydrolyzing the mixture with a base or acid wash having a sufficiently different density so that two liquid phases form, and separating the two liquid phases.
Description
The present invention relates to separate the component in the complex mixture with partially recycled organic compound and mineral compound.Especially the present invention relates to from liquid hydrocarbon solution, such as the method for the alcoholate of separating titanium and vanadium the solution that generates from preparation olefin polymerization catalysis precursor.
Producing thermoplastic polymer with rudimentary alpha-olefine polymerizing is the industry with remarkable commercial significance.The polymerisate of this method, be the important commercial material such as polypropylene, polyethylene and ethylene/propene copolymer, this is because the desirable processing characteristics that polymer phase has low price and they.Because polyethylene polymer only exists with a kind of spatial form, so the polymerization of ethene is uncomplicated relatively.Because the side alkyl of olefinic monomer, higher alpha-olefin, form the polymkeric substance of several spatial forms such as propylene.The spatial form of the polymkeric substance of preparation will influence for example polyacrylic price and value greatly.The most business-like polypropylene is crystal and high stereospecific and generally is isotactic.Not that stereoregular polypropylene is called atactic and is not crystalline.Seldom need this amorphous polymer, and if have certain amount, must before having commercial attractability, remove polypropylene usually by extraction.In recent commercial polypropylene was produced, the reason that in fact must follow was economically used the polymerizing catalyst that enough activity is arranged and produce the high stereospecific product, does not need extraction or deliming step can produce the polypropylene that can accept characteristic.
This active, stereoregular Preparation of catalysts is quite complicated process, conflicts mutually with many components in the custom of being everlasting is called the preparation process of olefin polymerization procatalyst.This catalyst precursor often is solids containing titanium and usually contains a part of magnesium and halogen, especially chlorine.For poly production, procatalyst often is to contain the vanadium solid.This procatalyst is narration to some extent in numerous patents neutralize other reference, depends on required special catalyst in the variation aspect the change chemical property.One class procatalyst is from magnesium compound, usually is pure magnesium compound and titanic halogenide at the halohydrocarbons reaction thinner and usually is that reaction generates in the presence of the electron donor of aromatic monocarboxylate or dicarboxylic acid alkyl ester.
Procatalyst generally is a solid matter, and is easy to isolate from its preparation medium.Left waste product is a liquid substance, and contain some unreacted heavy metal halides at least, halon, for example title complex of chlorobenzene, unreacted electron donor and various halogenated alcoholate compound or they and other chlorohydrin compound or aromatic ester.
There is very big handling problem in the waste product that obtains in the Preparation of Catalyst in the past, and this problem also is unfavorable for the economic problems of polymerization process.Advantageously can separate the composition and the recovery of this waste streams and reuse valuable especially composition in the product, such as titanium tetrachloride and halohydrocarbons reaction thinner.
A kind of method of separating component is disclosed in people's such as Potter the United States Patent (USP) 5242549.This reference provides and will separate the method separation waste product component that solvent is added in the waste product, isolates liquid components then with distillating method.The waste streams that this patent produces contains alcoholate and the chlorohydrin and their title complex of titanium compound such as titanium, and they are dissolved in separates in the solvent.Separate solvent the most habitual be aromatic halohydrocarbons such as chlorobenzene and toluene(mono)chloride.If to a kind of treatment process, metallic compound can become solid to be removed from separate solvent, and separates solvent and can be further purified to reuse in still-process, can see big economic benefit.
In order from liquid hydrocarbon mixture, to separate and reclaim the alcoholate of titanium and vanadium, the present invention proposes new method.In example of the present invention, hydrocarbon mixture is higher than the alkaline aqueous solution hydrolysis of liquid hydrocarbon with density, and metallic compound becomes oxyhydroxide and is enriched in the alkali aqueous solution like this, forms two kinds of liquid phases.Below contain the alkaline aqueous solution that metal hydroxides is arranged mutually, top is metal-free liquid hydrocarbon mutually substantially.Separate two phases, hydrocarbon phase is further purified as required.
In another specific examples of the present invention, metal alcoholate comprises the alcoholate or the chlorohydrin of titanium or vanadium.
In another specific examples of the present invention, hydrocarbon is the hydrochloric ether such as dichlorobenzene or toluene(mono)chloride, or hydrocarbon is a dimethylbenzene.
In another specific examples of the present invention, liquid hydrocarbon mixture acidic solution hydrolysis is so that heavy metal accumulation in acidic solution, forms two-phase mixture.Separate two phases, liquid hydrocarbon is further purified as required.
Method of the present invention comprise from the liquid hydrocarbon solution separating and reclaim the heavy metal alcoholate, such as the alcoholate of titanium and the alcoholate of vanadium, redistillation thereafter or purification of liquid hydrocarbon.Though this method can be widely used in and the separating of the irrelevant this mixture of its generation, this method can be applicable to remove excessive titanium alcoholate such as what narrate from separate solvent waste product stream especially in US5242549.The chlorohydrination thing that the waste product of this patents state stream (being stream 22 in this patent) comprises the alcoholate of titanium and titanium with separate solvent dichlorobenzene, toluene(mono)chloride or dimethylbenzene.Utilize the present invention, this waste streams can be processed to remove titanium compound, and the purification of liquid hydrocarbon is to re-use in this flow process.
The logistics of being handled by method of the present invention is the alcoholate and the chlorohydrination thing of mixture, particularly these metals of the compound of titanium in liquid hydrocarbon and vanadium.This solution also can contain metal alkoxide and other metal alkoxide or and the various title complexs of aromatic ester.Liquid hydrocarbon can be any useful separated solvent such as halohydrocarbon or aromatic hydrocarbon such as dimethylbenzene.The typical solvent that separates is narrated in US5242542.To all olefine polymerizing process, the processing of this waste streams has brought environmental hazard and sizable financial loss has been arranged.The recovering liquid hydrocarbon has the great economy interests with re-using in the production of all olefin polymerization procatalysts.In addition, reclaim solid titanium and vanadium compound also provide the procatalyst production technique with further processing or eliminating vital interests.
Method of the present invention comprises the hydrolysis phase, separates and removes metallic compound, optionally subsequently is further purified liquid hydrocarbon to remove other impurity.Hydrolysis is that available alkali cleaning can be finished with pickling again.With alkali cleaning is preferred scheme.Can carry out distillation or other purifying of liquid hydrocarbon with any method easily.
The liquid hydrocarbon streams of purifying can re-use in beginning to produce the system of waste streams then.For example, if the present invention is used for handling waste streams 22 among the patent US5242549, the hydrocarbon of purifying then can be as separation solvent (stream 4) circulation again of same Patent.
For the basic hydrolysis of solution, must select basic solution suitable, that will react with all metallic compounds carefully.If the metallic compound that is removed is a titanium compound, titanium hydroxide will become solid and precipitate in alkaline solution so.Therefore, alkaline solution density should be bigger than organic phase, and alkaline solution can form heavier liquid partly by organic phase and at reactor bottom like this.Solid precipitation is deposited in the alkaline solution of reactor bottom then.Most then metal-free organic phase can be discharged from reactor top, and further purifying as required.The major advantage of basic hydrolysis is that the bottom of containing the reactor of solid precipitation can be discharged and mutually through seldom processing or do not carry out additional processing and dispose.
On the other hand, vanadium hydroxide is generally solvable in alkaline aqueous solution.Therefore, will in basic solution, form vanadium compounds, but will not have the attendant advantages of shape solid precipitation.If use the inventive method to remove vanadium compounds, alkali must further be handled to remove the solid vanadium mutually then.
Mainly relevant with the basic solution that forms the solid situation in preparation is that alkaline solution density should be bigger than liquid hydrocarbon to be processed.Alkaline solution also should contain need and the superstoichiometric oxyhydroxide of contained whole heavy metals reactions in treatment soln.Alkaline solution should fully dilute so that solid chemical compound forms and can be easy to the slurries removed at the bottom of hydrolysis reactor.Desired solids content depends on from the equipment of reactor pumping slurries in the slurries.
When processing was dissolved in the solution of titanium compound of halohydrocarbon, the aqueous solution contained 4%-25% and has found it is effective mineral alkali.Sodium hydroxide is preferred, but potassium hydroxide or other mineral alkali also can use.The accurate amount that is contained in sodium hydroxide in the alkaline solution or potassium will depend on the amount that is contained in titanium compound in the hydrocarbon and the density of hydrocarbon.As mentioned above, the aqueous solution content of alkaline solution mainly is the density decision by required alkaline titanium product slurry.
In the notion that laboratory scale is confirmed, the material of 100ml such as logistics 22 in patent US5242549 slowly is added in 100ml 20% weight sodium hydroxide solution.The titanium compound continuous precipitation becomes white solid at denseer caustic alkali in mutually, and formation can be easy to isolating organic phase.Reclaim organic phase and distillation then to generate enough pure material to be used as the separation solvent in the above-mentioned patent separation method.
If use acid hydrolysis, different factors will determine the component of required acid solution.In acid hydrolysis, prevent to form solid if keep enough pH values (general＜1), metallic compound will be dissolved in the acid mutually of reactor.Opposite with alkaline hydrolysis, the density of acid solution does not need bigger than organic phase, and this is because with irrelevant at reactor bottom formation solid.But the density of acid solution should have enough difference with organic phase, makes and obviously form two phases during hydrolysis reaction.Preferred acidic solution is mineral acid, such as HCl or H
2SO
4After the hydrolysis, reaction container bottom and top liquid can be removed respectively.Generally, acid solution must neutralize before blowing, and will form metal solid separable and that handle.Metal-free hydrocarbon liquid will be as using basic hydrolysis to distill and purifying with same procedure again substantially.
The present invention can be finished by those skilled in the art in the variation of this sequence of steps narrated and component, and these variations are included in the spirit of the present invention of claims definition.
Claims (14)
1. from liquid hydrocarbon mixture, remove the method for titanium or vanadium alcoholate, comprising:
The alkaline aqueous solution processing hydrocarbons mixture that is higher than the density of hydrocarbon mixture with density, therefore, the upper strata comprises the heavy metal hydroxide that comprises alkaline aqueous solution and formation during the liquid hydrocarbon of essentially no metal and lower floor are mutually in mutually; With
From described supernatant liquid hydrocarbon phase, separate described lower floor alkaline aqueous solution phase.
2. the method for claim 1 further comprises the liquid hydrocarbon phase of purifying.
3. the process of claim 1 wherein that alcoholate is the alcoholate of titanium.
4. the process of claim 1 wherein that alcoholate is the alcoholate of vanadium.
5. the method for claim 2, wherein liquid hydrocarbon is a halogenated aromatic hydrocarbons.
6. the method for claim 5, wherein the liquid halogenated aromatic hydrocarbons is dichlorobenzene or toluene(mono)chloride.
7. the method for claim 2, wherein liquid hydrocarbon is a dimethylbenzene.
8. remove the method for the alcoholate of titanium or vanadium from liquid hydrocarbon mixture, comprising:
With acidic solution processing hydrocarbons mixture, therefore form the mixture of two phases, first comprises that mutually the liquid hydrocarbon and second that does not have metal substantially includes the acid solution of dissolved heavy metal mutually; With
Be separated from each other two phases and reclaim hydrocarbon phase.
9. the method for claim 8 further comprises the purification of liquid hydrocarbon phase.
10. the method for claim 8, wherein alcoholate is the alcoholate of titanium.
11. the method for claim 8, wherein alcoholate is the alcoholate of vanadium.
12. the method for claim 9, wherein liquid hydrocarbon is a halogenated aromatic hydrocarbons.
13. the method for claim 12, wherein halogenated aromatic hydrocarbons is dichlorobenzene or toluene(mono)chloride.
14. the method for claim 9, wherein liquid hydrocarbon is a dimethylbenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96121938 CN1161318A (en) | 1995-11-01 | 1996-10-31 | Method for removal of metal (Ti or V) alkoxide compounds from liquid hydrocarbon |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US548291 | 1995-11-01 | ||
| CN 96121938 CN1161318A (en) | 1995-11-01 | 1996-10-31 | Method for removal of metal (Ti or V) alkoxide compounds from liquid hydrocarbon |
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| Publication Number | Publication Date |
|---|---|
| CN1161318A true CN1161318A (en) | 1997-10-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96121938 Pending CN1161318A (en) | 1995-11-01 | 1996-10-31 | Method for removal of metal (Ti or V) alkoxide compounds from liquid hydrocarbon |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420437A (en) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | Recovery processing method of titanium-containing waste liquid |
| 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 |
| CN107952260A (en) * | 2016-10-14 | 2018-04-24 | 张瑞永 | Method for extracting and recovering chemicals from carbon black after cracking waste rubber |
| CN112707561A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Treatment method of titanium-containing waste liquid |
-
1996
- 1996-10-31 CN CN 96121938 patent/CN1161318A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420437A (en) * | 2012-05-17 | 2013-12-04 | 中国石油化工股份有限公司 | Recovery processing method of titanium-containing waste liquid |
| CN103420437B (en) * | 2012-05-17 | 2015-10-07 | 中国石油化工股份有限公司 | A kind of recovery and treatment method of titaniferous waste liquid |
| 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 |
| 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 |
| CN107952260A (en) * | 2016-10-14 | 2018-04-24 | 张瑞永 | Method for extracting and recovering chemicals from carbon black after cracking waste rubber |
| CN112707561A (en) * | 2019-10-25 | 2021-04-27 | 中国石油化工股份有限公司 | Treatment method of titanium-containing waste liquid |
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