CN1007983B - Be dissolved in the new nickeliferous composition of hydro carbons - Google Patents
Be dissolved in the new nickeliferous composition of hydro carbonsInfo
- Publication number
- CN1007983B CN1007983B CN 85101877 CN85101877A CN1007983B CN 1007983 B CN1007983 B CN 1007983B CN 85101877 CN85101877 CN 85101877 CN 85101877 A CN85101877 A CN 85101877A CN 1007983 B CN1007983 B CN 1007983B
- Authority
- CN
- China
- Prior art keywords
- nickel
- new
- composition
- nickeliferous
- acetic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The new solubleness of nickeliferous composition in hydro carbons is very big.The method for making of said composition is to use a kind of divalent inorganic nickel compound at least, and at least a halogenated acetic acid and at least a structural formula are R
1COOR
2(R
2Be hydrogen atom or alkyl, R
2Be alkyl) the carboxylicesters phase reaction and make.
The new nickeliferous composition that reaction obtains can mix in hydrocarbyl aluminium halide, as the dimerizing olefins catalyst for reaction.
Description
The objective of the invention is to prepare a kind of new nickeliferous composition.This composition is dissolved in hydro carbons and contains a halogenated acetic acid negatively charged ion.
The metal carboxylate of nickelous is derived from the short chain carboxy acid, be carbonatoms in the carboxylic acid less than 5, for example: acetate, propionic salt, butyrates and derived from the halogenated derivative of above-mentioned carboxylic acid such as chloracetate, dichloroacetate, trichloroacetate, trifluoroacetate.Known they under the normal temperature state, in fact be insoluble to hydro carbons.In contrast, long-chain carboxylic acid's salt of nickelous, promptly carbonatoms and preferably is with a side chain greater than 5 in the carboxylic acid, then is dissolved in hydro carbons as 2 ethyl hexanoic acid nickel.
United States Patent (USP) discloses the halogenated acetic acid negatively charged ion dissolved method that links to each other with nickel that makes for No. 4316851, this method is to utilize a kind of mixing salt, nickel valence link links to each other with the halogenated acetic acid negatively charged ion in mixing salt, and another valence link and carbon atom quantity link to each other greater than 5 long-chain carboxylic acid's negatively charged ion.
But the negatively charged ion that increases a long-chain carboxylic acid in halogenated acetic acid nickel derivative can improve productive expense, sometimes use also inconvenient, for example in an application example, the nickel salt that contains the halo acetate anion obtains being used for the catalyzer of alkene liquid phase dimerization reaction with the aluminum alkyl halide reaction in hydrocarbon solution.After dimerization reaction finishes, be a kind of method of removing mineral compound in the medium with the aqueous sodium hydroxide solution extraction.In this step, long-chain carboxylic acid's negatively charged ion is owing to the surfactivity effect of its sodio-derivative produces foam, and this separates biphase is disadvantageous.In addition, the dispersion of the nickel oxide of sodium hydroxide and catalyst reaction generation has also degenerated.
The purpose of this invention is to provide the new nickeliferous method for compositions of preparation.Said composition is dissolved in hydro carbons and contains the halo acetate anion.Present method is not used and is contained the above carboxylate anion of 5 carbon atoms.
Find that at least a divalent inorganic nickel compound and a kind of halogenated acetic acid react the back and form a kind of fluid composition that is dissolved in hydro carbons in carboxylicesters.This is beyond thought, because inorganic nickel derivative can generate the halogenated acetic acid nickel of expectation, and the latter is insoluble to hydro carbons fully under normal temperature condition.
According to the present invention, inorganic nickel compound for example can be: nickelous carbonate, hydrogen-carbonate nickel, basic nickel carbonate (hydroxyl nickelous carbonate), nickel hydroxide or nickel oxide.
Halogenated acetic acid for example can be: monochloroacetic acid, fluoroacetic acid, dichloro-acetic acid, three chloro acetic acid, two fluoro acetic acid or three fluoro acetic acid.
The general formula of carboxylicesters is R
1COOR
2, R wherein
1And R
2Be alkyl, R
1It also can be hydrogen atom.More precisely, R
1And R
2Can be to contain 1-20 carbon atom band alkyl side chain or straight chain, to contain 1-5 carbon atom for well, also can be the aryl that contains 6-9 carbon atom, R
1It also can be hydrogen atom.For example: methyl acetate, methyl-formiate, n-butyl acetate, isobutyl acetate, methyl propionate, isopropyl formate.
The ratio of halogenated acetic acid and nickel is the 0.1-2 mole, and preferably 0.5-1.5 moles of halogenated acetic acid is to every grammeatom nickel.
The usage ratio of above-mentioned carboxylicesters is that every grammeatom nickel rises ester with 0.1-01, the most handy 0.2-2 liter.
Can add halogen atom not in the mixture of above-mentioned three kinds of components but contain the above carboxylic acid of 3 carbon atoms, for example: butyric acid, lauric acid, 2 ethyl hexanoic acid, stearic acid.But with the discovery contrast in No. the 4316851st, the United States Patent (USP), adding carboxylic acid is not to make composition requisite in the hydro carbons dissolving, and on the other hand, the quantity of carboxylic acid is less than 1 in acid/nickel mol ratio, with the acid of 0.1-0.9 mole to every grammeatom nickel for well.
Preferred embodiment of the present invention is included under the vigorous agitation in the mixture of the nickel compound of above-mentioned formation and ester and adds halogenated acetic acid.
Under pressure selected, the temperature of reaction of mixture can be from room temperature the boiling point to ester, the reflux temperature that is preferably in ester is to remove carbonic acid gas and the water that dereaction generates, reaction continues to all nickel and dissolves fully, halogenated acetic acid all consumes, and till water and/or carbonic acid gas no longer produced, not halogenous carboxylic acid can add before halogenated acetic acid adds, also can add, even add at reaction end in any moment of reaction.
Reaction can be carried out in hydro carbons.Said hydro carbons, for example: pentane, hexane, heptane, octane or its isomer and their mixture, or benzene, toluene, dimethylbenzene.Can react hydrocarbon middle or reaction end adding different quantities in the beginning of reaction, hydrocarbon helps to take off the water that reaction generates.
The present invention also relates to catalyst composition: (a) the above-mentioned nickeliferous composition of solubility and (b) hydrocarbyl aluminium halide, its quantitative proportion be every grammeatom nickel to the 1-50 mole, best 2-20 mole hydrocarbyl aluminium halide.
The present invention also relates to the application of above-mentioned catalyst composition, promptly as the catalyzer of liquid phase olefin dimerization reaction, suitable polymerization temperature is 0-60 ℃.
Alkene, for example ethene, propylene or butylene.
The amount of catalytic composition is preferably 1,000,000/5-500(weight).
The present invention is by following example explanation, but scope of the present invention is not limited to following example.
Example 1
10 grams (8 * 10
-2Mole) basic nickel carbonate NiCO
3Ni(OH)
2H
2O, 150 milliliters of N-BUTYL ACETATEs and 6 milliliter (8 * 10
-2Mole) trifluoroacetic mixture heating up refluxed 2 hours, removed the water that dereaction generates.
Obtain a kind of green micellar solution, its available any amount of heptane dilution and do not produce precipitation.
Example 2
Repeat example 1, but add 4.4 grams (5 * 10 again
-2Mole) butyric acid.The green solution that obtains can not produced precipitation by the dilution of the heptane of any ratio.
Example 3
Repeat example 2, but with 8 * 10
-2The Tricholroacetic Acid of mole replaces trifluoracetic acid.Obtain the micellar solution of same-type.It almost contains the nickel of whole addings, and can be by the various hydrocarbon dilutions of any ratio.
Example 4
This example is not an integral part of the present invention.It has been illustrated as and has obtained nickeliferous solution, the essential ester that uses.
The above-mentioned nickelous carbonate of 10 grams, 6 milliliters of trifluoracetic acids reflux in 200 milliliters of hexanes, carbonic acid gas is overflowed rapidly, but medium is still colourless fully, and the insolubles of generation is through being accredited as two trifluoroacetic acid nickel (CF
3COO)
2
Example 5
Repeat example 2, but replace butylacetate with 150 milliliters of methyl-formiates.The green solution that obtains contains most of nickel that adds.
Example 6
Method is identical with example 2, but butylacetate is replaced by ethyl butyrate.Nickel and available heptene that the green solution that obtains contains whole addings are diluted to any degree.
Example 7
The solution of example 1 gained is used for the butene dimerization reaction.
Under 45 ℃, but continuously in the tandem reactor system of two 0.25 liter and attemperation, add the C that contains 72% n-butene
4Hydrocarbon-fraction (100 gram/time), be dissolved in heptane example 1 composition forms nickel (0.1 mmole/time) and be dissolved in the ethyl aluminum dichloride (1.5 mmoles/time) of heptane.For removing the inorganics in the catalyzer, respectively be 0.25 liter of placed in-line reactor by effusive reactant in second reactor by two, use earlier 18%(weight) the aqueous sodium hydroxide solution processing, wash with water continuously again.
The sedimentation difficult problem does not all take place in each phase, and the hydrocarbon phase of recovery has been taken off salt fully.The nickel oxide precipitation that generates with the sodium hydroxide solution effect is disperseed fully, therefore is easy to take off in hydrocarbon phase.
In control examples, replace the composition of example 2 to test with trifluoracetic acid 2 ethyl hexanoic acid nickel mixing salt.The a large amount of foams that produce in the water washing process have hindered smooth sedimentation, in addition, find the precipitation of nickel oxide between aqueous sodium hydroxide solution and hydro carbons two-phase, thereby are difficult to it is removed.
Example 8
Feed the cut (1000 gram/time) that contains 95% propylene under 40 ℃ and 2 MPa pressure in two 9 liters tandem reactor continuously, the ethyl aluminum dichloride (5.5 millis are that/time in the least) that is dissolved in heptane is dissolved in the nickel of example 2 compositions of heptane (0.55 mmole/time).Under stable operational condition, the transformation efficiency of first reactor is 90.1%.Total conversion rate is 96.5%.Reactant is handled with 20% aqueous sodium hydroxide solution, then washing.Hydrocarbon phase and water are very easy to be distinguished, and the precipitation nickel oxide that generates with the sodium hydroxide effect disperses fully, therefore is easy to by removing in the hydrocarbon phase.
Example 9
Repeat example 8, but the catalytic composition of use-case 6 replaces the catalytic composition of example 2.The transformation efficiency of first reactor is 89%, total conversion rate 95.5%.The same with example 8, be easy to separate.
Claims (8)
1, a kind of new nickeliferous composition that is dissolved in hydro carbons is characterized in that said compound is by what obtain after the following compounds reaction
The mineral compound of nickelous,
Halogenated acetic acid and
General formula is R
1COOR
2Carboxylicesters, R wherein
1Being hydrogen, also can be the straight chained alkyl that contains 1-3 carbon atom; R
2It is the straight chained alkyl that contains 1-4 carbon atom; Wherein
Every grammeatom nickel in the mineral compound is with halogenated acetic acid 0.1-2 mole, with carboxylicesters 0.1-10 liter.
2, according to the new nickeliferous composition of claim 1, its preparation method comprises the halogenated acetic acid 0.5-1.5 mole of the every grammeatom nickel in the mineral compound, with carboxylicesters 0.2-2 liter.
3, according to the new nickeliferous composition of claim 1, its preparation method comprises the nickelous carbonate as the mineral compound of nickel, hydrogen-carbonate nickel, basic nickel carbonate, nickel oxide or nickel hydroxide.
4, according to the new nickeliferous composition of claim 1, its preparation method comprises the basic nickel carbonate as the mineral compound of nickel.
5, according to the new nickeliferous composition of claim 1, its preparation method comprises the trifluoroacetic acid as halogenated acetic acid.
6, according to the new nickeliferous composition of claim 1, its preparation method also comprises: with contain 3 not halogen-containing carboxylic acid reactions more than the carbon atom at least, the ratio of this not halogen-containing carboxylic acid and every grammeatom nickel is the 0.1-0.9 mole.
7, according to the new nickeliferous composition of claim 1, the R in its preparation method in the used starting raw material
1Be hydrogen or the alkyl that contains 2 or 3 carbon atoms, R
2It is the alkyl that contains 2 or 4 carbon atoms.
8, the application of the new nickeliferous composition of claim 1 is characterized in that being used for mixing the catalyzer of hydrocarbyl aluminium halide as dimerized cleans method in liquid phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85101877 CN1007983B (en) | 1983-11-29 | 1985-04-01 | Be dissolved in the new nickeliferous composition of hydro carbons |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8319183A FR2555570B1 (en) | 1983-11-29 | 1983-11-29 | NEW COMPOSITION OF BIVALENT NICKEL SOLUBLE IN HYDROCARBONS |
| CN 85101877 CN1007983B (en) | 1983-11-29 | 1985-04-01 | Be dissolved in the new nickeliferous composition of hydro carbons |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85101877A CN85101877A (en) | 1987-01-10 |
| CN1007983B true CN1007983B (en) | 1990-05-16 |
Family
ID=25741513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85101877 Expired CN1007983B (en) | 1983-11-29 | 1985-04-01 | Be dissolved in the new nickeliferous composition of hydro carbons |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1007983B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580774A (en) * | 2011-01-04 | 2012-07-18 | 中国石油化工集团公司 | Unsaturated polymer hydrogenation catalyst and preparation method thereof |
-
1985
- 1985-04-01 CN CN 85101877 patent/CN1007983B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN85101877A (en) | 1987-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1071727C (en) | Olefin production | |
| CN1090535C (en) | Olefin production | |
| US4538018A (en) | Surface conditioning in olefin dimerization reactors | |
| US8629080B2 (en) | Hydrated niobium oxide nanoparticle containing catalysts for olefin hydration | |
| CN111094219B (en) | In-line process for preparing antifouling agent cocatalyst for ethylene oligomerization | |
| RU2128159C1 (en) | Method of preparing c2-c11 carboxylic acids or esters thereof | |
| FR2984311A1 (en) | PROCESS FOR THE PRODUCTION OF OCTENS USING THE DIMERISATION OF ETHYLENE TO BUTENES AND DIMERIZATION OF BUTENES IN OCTENES | |
| KR20100113534A (en) | Method for preparing linear alpha-olefins | |
| JPH09323943A (en) | Production of vinyliudeneolefin | |
| AU725208B2 (en) | Process for preparing butene oligomers from Fishcher- Tropsch olefins | |
| CN1117774C (en) | Improved method for preparing isobutene rubber by applying activated alkylaluminium halide | |
| CN101252990B (en) | Process for the preparation of linear alpha-olefins and catalyst used therein | |
| CN1117628C (en) | Bimetallic catalyst for homogeneous methanol carbonylation and its prepn | |
| JPS6360042B2 (en) | ||
| US3954668A (en) | Nickel containing olefin oligomerization catalyst | |
| US4777314A (en) | New nickel composition soluble in hydrocarbons and use thereof | |
| CN1007983B (en) | Be dissolved in the new nickeliferous composition of hydro carbons | |
| US3992323A (en) | Olefin polymerization catalyst | |
| EP0144936B2 (en) | Production of carboxylic acids from alcohols | |
| WO1992006059A1 (en) | Process for making olefins | |
| US5166114A (en) | Ethylene dimerization and catalyst therefor | |
| US5260499A (en) | Ethylene dimerization and catalyst therefor | |
| JPH07173086A (en) | Method for producing dialkylbiphenyl compounds | |
| US4356126A (en) | Carbonylation of alkanols and/or aliphatic ethers | |
| JP2610490B2 (en) | Solid acid catalyst for alkylation reaction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C13 | Decision | ||
| GR02 | Examined patent application | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |