CN1422839A - Preparation method for active chromium of organic acid - Google Patents
Preparation method for active chromium of organic acid Download PDFInfo
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- CN1422839A CN1422839A CN 01140236 CN01140236A CN1422839A CN 1422839 A CN1422839 A CN 1422839A CN 01140236 CN01140236 CN 01140236 CN 01140236 A CN01140236 A CN 01140236A CN 1422839 A CN1422839 A CN 1422839A
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Abstract
The invention provides a method to prepare active organic-acid chrome. It makes trivalent chrome compound directly react with iso-octoix acid in the reactor with stirring and heating unit. It adds a little easy-to-volatile solvent like hexyl alkane or heptane to reduce the viscosity of reactant before stirring and raising temperature. It gradually raises the temperature to make chrome salt and organic carboxylic acid react, which solves the solid and evaporates out easy-volatile component and water and finally extrudes a little water to make the iso-octoic acid chrome with catalysis activity.
Description
Technical field
The present invention relates to a kind of preparation method of active chromium of organic acid, relate in particular to the preparation method of active trivalent chromium of organic acid.
Background technology
Chromium of organic acid (particularly trivalent chromium of organic acid) is a kind of important chromic salts, and its solubleness in non-polar solvent is big, dissolution rate is fast, often is used as with chromium (Cr
3+) be the raw material of catalyzer, as ethylene oligomerization and imide ring oxidizing reaction (imide-oxirane reaction) etc.Trivalent chromium has the ability of great generation coordination compound, is 6 o'clock in ligancy, has the regular octahedron configuration, Cr
3+Be positioned at octahedra center.Be used as the Cr of catalyzer
3+Free coordination need be arranged, promptly need in the preparation process of chromium of organic acid other ligand is shifted out coordination, have the Cr of catalytic activity with formation
3+
U.S. Pat P3,968,135 and USP3,962,182 disclose active chromic salt the preparation method, this method at first is converted into Sodium isooctanoate with isocaprylic acid, with the reactant aqueous solution of chromic salts, after alkali cleaning, washing, obtain three hydration isocaprylic acid chromium, and then be heated in the presence of the organic carboxyl acid more than 140 ℃ again to obtain having the chromium of organic acid of catalytic activity, problems such as there is the preparation process complexity in this method, and energy consumption height and product yield are low.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of active trivalent chromium of organic acid, this preparation method have simple, the low power consumption and other advantages of technology.
Active chromium of organic acid Cr of the present invention (RCOO)
3The preparation method, comprise trivalent chromium compound is mixed with organic carboxyl acid RCOOH, stir and to be warming up to 100-140 ℃ of reaction down down, treat to be warming up to after the chromium cpd solid dissolves fully 150-220 ℃ keep 0-5 hour, preferably be warming up to 190-210 ℃ of maintenance and made in 0-1 hour.Prepared organic acid chromium has following essential feature:
1, under this product room temperature is deep green homogeneous phase oily liquids.
2, can dissolve each other fully with organic solvent.
3, reaction has advantages of high catalytic activity to ethylene trimerization system 1-hexene.
Method of the present invention makes chromium cpd and organic carboxyl acid reaction by improving temperature gradually, thereby makes the dissolving of chromium cpd solid and steam volatile components and water, and then improves method of temperature and drive coordinated water out of, thereby makes active chromium of organic acid.
Soluble chromium compound of the present invention is hydration chromium chloride, hydrated chromium oxide, chromium hydroxide, chromium nitrate or chromium acetate etc.
R of the present invention is for containing aliphatic group, aryl, cycloalkyl group, aralkyl or the alkaryl of 5 carbon atoms at least.The aliphatic group, aryl, cycloalkyl group, aralkyl or the alkaryl that preferably contain 5-10 carbon atom.More preferably pentyl, 2-ethyl pentyl group, octyl group or nonyl.
For reducing the viscosity of reactant, before stirring intensification, can in reaction mixture, add solvent C
5-C
8Alkane, benzene or toluene.The add-on of solvent is: the volume ratio of solvent and organic carboxyl acid is 1/10-1/1.Described C
5-C
8Preferred hexane of alkane or heptane.
The mol ratio of organic carboxyl acid of the present invention and chromium cpd is at least 3/1, considers to be preferably 3/1-5/1 from economic angle.
Can a step obtain active chromium of organic acid with method of the present invention, the gained active chromium of organic acid can directly react as catalyst activity catalytic ethylene trimerization system 1-hexene.
Embodiment
The following examples will help to illustrate the present invention, but not limit to its scope.
It is as follows as the condition of ethylene trimerization system 1-hexene catalysts to estimate chromium of organic acid: get the chromium of organic acid 0.001mol (in chromium) that makes, be diluted to 100 milliliters with heptane, the concentration of chromium is the 0.01mmol/ milliliter in this solution.Make triethyl aluminum equally, 2, the 5-dimethyl pyrrole, each 100 milliliters of the n-heptane solutions of tetrachloroethane, concentration is followed successively by triethyl aluminum 0.5mmol/ milliliter, and 2,5-dimethyl pyrrole 0.03mmol/ milliliter, tetrachloroethane 0.05mmol/ milliliter, stand-by.Be reflected in the tank reactor that 500 milliliters of bands stir and carry out.Before each reaction that reactor is clean with nitrogen replacement, add 100 milliliters of heptane, get the above-mentioned chromium of organic acid that makes, triethyl aluminum again, 2, the 5-dimethyl pyrrole, the n-heptane solution of tetrachloroethane adds reactor for each 1 milliliter.Feed ethene, begin to stir, and temperature of reaction is risen to 100 ℃ rapidly, begin reaction.Keep ethylene pressure in the reaction process at 5Mpa, reacted 30 minutes.Form with the gas chromatographic analysis product, calculate 1-hexene output and catalyst activity, its method of calculation are as follows:
The weight percentage of 1-hexene in the output of 1-hexene=product gross weight * products therefrom
In the output of catalyst activity=1-hexene/(weight * reaction times of chromium ion), promptly catalytic activity is the total amount of the ethylene tripolymer (1-hexene) that per hour generates of every gram chromium metal.
Embodiment 1:
Get 26.6 gram chromium chloride CrCl
3.6H
2O (0.1mol) packs in 1000 milliliters the flask, and 43.2 gram (0.3mol) 2 ethyl hexanoic acids (isocaprylic acid) are poured into wherein, begins to stir and heating, gradually temperature is risen to 120 ℃ of reactions.In this course, solid dissolves gradually, and solution becomes green, treat that solid dissolves fully after, continue elevated temperature, temperature is risen to 200 ℃ gradually.In this course, HCl, water are steamed.After temperature is 200 ℃, stop heating, reactant is cooled to room temperature makes thick green liquid 46.2 grams.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 310 kilograms of 1-hexenes for every gram chromium.
Embodiment 2:
Keep after being warmed up to 200 ℃ 0.5 hour, all the other conditions obtain product 45.5 grams with embodiment 1.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 330 kilograms of 1-hexenes for every gram chromium.
Embodiment 3:
Except that final step is warmed up to 210 ℃, all the other conditions obtain product 45.0 grams with embodiment 1.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 310 kilograms of 1-hexenes for every gram chromium.
Embodiment 4:
Except that temperature of reaction is 110 ℃, all the other conditions obtain product 46.5 grams with embodiment 1.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 320 kilograms of 1-hexenes for every gram chromium.Embodiment 5:
Except that temperature of reaction is 130 ℃, all the other conditions are with embodiment 1, and products obtained therefrom 46.5 restrains.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 300 kilograms of 1-hexenes for every gram chromium.
Embodiment 6:
Get 26.6 gram chromium chloride CrCl
3.6H
2O (0.1mol) packs in 1000 milliliters the flask, and 50.4 gram (0.35mol) 2 ethyl hexanoic acids are poured into wherein, and all the other conditions obtain product 52.2 grams with embodiment 1.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 310 kilograms of 1-hexenes for every gram chromium.
Embodiment 7:
Get 26.6 gram chromium chloride CrCl
3.6H
2O (0.1mol) packs in 1000 milliliters the flask, and 57.6 gram (0.4mol) 2 ethyl hexanoic acids are poured into wherein, and all the other conditions obtain product 59.0 grams with embodiment 1.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 315 kilograms of 1-hexenes for every gram chromium.
Embodiment 8:
Except that adding before stirring intensification 10 milliliters of heptane, all the other conditions obtain product 45.0 grams with embodiment 1.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 300 kilograms of 1-hexenes for every gram chromium.
Embodiment 9:
Except that adding before stirring intensification 20 milliliters of benzene, all the other conditions obtain product 44.2 grams with embodiment 1.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 320 kilograms of 1-hexenes for every gram chromium.
Embodiment 10:
Replace outside the chromium chloride divided by the 0.1mol chromium hydroxide, all the other conditions obtain product 47.3 grams with embodiment 1.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 305 kilograms of 1-hexenes for every gram chromium.Embodiment 11:
Replace outside the chromium chloride divided by the 0.1mol chromium nitrate, other condition obtains product 46.8 grams with embodiment 1.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 300 kilograms of 1-hexenes for every gram chromium.Embodiment 12:
Replace 2 ethyl hexanoic acid and final step to be warmed up to outside 190 ℃ divided by the own carboxylic acid of 0.3mol, other condition is with embodiment 1.Obtain product 35.2 grams.This product is used for the reaction of catalyzed ethylene trimerization system 1-hexene, and its activity per hour generates 285 kilograms of 1-hexenes for every gram chromium.
Claims (10)
1, a kind of active chromium of organic acid Cr (RCOO)
3The preparation method, comprise trivalent chromium compound mixed with organic carboxyl acid RCOOH, stir and to be warming up to 100-140 ℃ of reaction down down, treat to be warming up to after the chromium cpd solid dissolves fully 150-220 ℃ of maintenance and made in 0-5 hour.
2, the preparation method of chromium of organic acid according to claim 1 is characterized in that described chromium cpd is hydration chromium chloride, hydrated chromium oxide, chromium hydroxide, chromium nitrate or chromium acetate.
3, the preparation method of chromium of organic acid according to claim 1 and 2 is characterized in that described R is for containing aliphatic group, aryl, cycloalkyl group, aralkyl or the alkaryl of 5 carbon atoms at least.
4, the preparation method of chromium of organic acid according to claim 3 is characterized in that described R is aliphatic group, aryl, cycloalkyl group, aralkyl or the alkaryl that contains 5-10 carbon atom.
5, the preparation method of chromium of organic acid according to claim 4 is characterized in that described R is pentyl, 2-ethyl pentyl group, octyl group or nonyl.
6,, it is characterized in that also can in stirring intensification forward reaction mixture, adding solvent C according to the preparation method of each described chromium of organic acid of claim 1-5
5-C
8Alkane, benzene or toluene.
7, the preparation method of chromium of organic acid according to claim 6, it is characterized in that the add-on of described solvent is: the volume ratio of solvent and organic carboxyl acid is 1/10-1/1.
8, according to the preparation method of claim 6 or 7 described chromium of organic acid, it is characterized in that described C
5-C
8Alkane is hexane or heptane.
9, according to the preparation method of each described chromium of organic acid of claim 1-8, it is characterized in that being warming up to 100-140 ℃ of reaction down, treat to be warming up to after the chromium cpd solid dissolves fully 190-210 ℃ and kept 0-1 hour.
10, according to the preparation method of each described chromium of organic acid of claim 1-9, the mol ratio that it is characterized in that described chromium cpd and organic carboxyl acid is 3/1-5/1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011402369A CN1186305C (en) | 2001-12-07 | 2001-12-07 | Preparation method for active chromium of organic acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011402369A CN1186305C (en) | 2001-12-07 | 2001-12-07 | Preparation method for active chromium of organic acid |
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| CN1422839A true CN1422839A (en) | 2003-06-11 |
| CN1186305C CN1186305C (en) | 2005-01-26 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8957235B2 (en) | 2011-12-12 | 2015-02-17 | Chevron Phillips Chemical Company Lp | Preparation of transition metal carboxylates |
| US9956548B2 (en) | 2011-12-12 | 2018-05-01 | Chevron Phillips Chemical Company Lp | Preparation of an olefin oligomerization catalyst |
| CN108440276A (en) * | 2018-05-10 | 2018-08-24 | 佛山市顺德区畅驰新材料有限公司 | A kind of organic carboxyl acid vanadic salts and preparation method thereof |
| CN114716309A (en) * | 2022-04-21 | 2022-07-08 | 烟台远东精细化工有限公司 | Process method and process device for producing chromium isobutyrate |
| CN114790136A (en) * | 2022-03-08 | 2022-07-26 | 中国石油天然气股份有限公司 | Preparation method and application of active trivalent organic chromium compound |
| TWI813976B (en) * | 2021-04-15 | 2023-09-01 | 行政院原子能委員會核能研究所 | Carboxylate, use of carboxylate for producing metal sulfide with nanostructure, method of preparation of metal sulfide with nanostructure, use of liguid medium ,and use of gaseous sulfuric source |
-
2001
- 2001-12-07 CN CNB011402369A patent/CN1186305C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8957235B2 (en) | 2011-12-12 | 2015-02-17 | Chevron Phillips Chemical Company Lp | Preparation of transition metal carboxylates |
| US9580453B2 (en) | 2011-12-12 | 2017-02-28 | Chevron Phillips Chemical Company Lp | Preparation of transition metal carboxylates |
| US9956548B2 (en) | 2011-12-12 | 2018-05-01 | Chevron Phillips Chemical Company Lp | Preparation of an olefin oligomerization catalyst |
| CN108440276A (en) * | 2018-05-10 | 2018-08-24 | 佛山市顺德区畅驰新材料有限公司 | A kind of organic carboxyl acid vanadic salts and preparation method thereof |
| TWI813976B (en) * | 2021-04-15 | 2023-09-01 | 行政院原子能委員會核能研究所 | Carboxylate, use of carboxylate for producing metal sulfide with nanostructure, method of preparation of metal sulfide with nanostructure, use of liguid medium ,and use of gaseous sulfuric source |
| CN114790136A (en) * | 2022-03-08 | 2022-07-26 | 中国石油天然气股份有限公司 | Preparation method and application of active trivalent organic chromium compound |
| CN114716309A (en) * | 2022-04-21 | 2022-07-08 | 烟台远东精细化工有限公司 | Process method and process device for producing chromium isobutyrate |
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| CN1186305C (en) | 2005-01-26 |
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Effective date of registration: 20170203 Address after: 100027 Beijing, Chaoyangmen, North Street, No. 22, No. Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Address before: 102500 Yanshan Phoenix Road, Fangshan District, No., No. 15 Patentee before: Beijing Research Inst. of Yanshan Petrochemical Corp. |
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Granted publication date: 20050126 |