Method of isomerization of alpha-olefins, linear internal olefins

 

Usage: petrochemistry. For virtually complete isomerization of linear alpha olefins in the linear internal olefins using the catalyst of the zeolite type pentasil containing the promoter isomerization representing monoxide Nickel in the amount of 1-10 wt.%. Effect: method allows to carry out the process without a significant increase in the reaction products of the content of branched internal olefins. 2 C. and 7 C.p. f-crystals, 3 tables.

The technical field to which the invention relates the Present invention relates to a method of isomerization of alpha-olefins, linear internal olefins with minimal skeletal isomerization.

Description of the prior art Olefins or alpha-olefins or internal olefins, and linear or branched structure, are used as drilling fluids used in the drilling of subterranean oil and gas wells, and also used in other applications of drilling fluids and drilling processes.

Researchers in the field of processing of the olefins are in the process of finding better, more effective and more economical ways of isomerization of alpha-olefins, linear internal olefins Betsy isomerization of olefins, however, such methods have not achieved success in reducing the number of branched olefins and/or, in addition, such methods other inherent disadvantages. For example, it is known that such synthetic hydrocarbons can be obtained by oligomerization of one or more olefinic monomers, for example, those which have a chain length of C2-C14.

In the known method of isomerization of olefins is used platinum catalyst deposited on the molecular sieve SAPO-11. In the patent Gee with TCS. (U.S. patent 5589442) included in the present description by reference, the catalyst is platinum/SAPO-11 is used for incomplete isomerization feedstock containing olefins, C14-C18preferably linear olefins, and more preferably normal alpha-olefins. The reaction product is a mixture of linear and branched olefins with a predominant content of internal olefins. The above catalyst is not effective to obtain a mixture, representing mainly completely linear, internal olefins. On the contrary, a significant portion of the product is a branched and/or alpha-olefins.

There are other ways, with similar disadvantages. microporous aluminophosphate catalyst in the presence of an inert gaseous hydrogen and alcantarea hydrocarbon mixtures.

Khare with TCS. (U.S. patent 5304696) describes the double bond isomerization of olefinic compounds by contact of olefinic compounds with sulfated dioxide-zirconium catalyst.

Heckelsberg (U.S. patent 3823572) describes the conversion of olefinic hydrocarbons, for example, propylene and/or butene, in at least one other olefinic hydrocarbons, for example, in isoamylene, in the process of catalytic conversion using simultaneous or sequential contacting of the catalyst of the reaction of olefin and catalyst skeletal isomerization.

Suzukamo with TCS. (Japan patent 01019027) discloses a method for the isomerization of olefins in sustainable internal olefins in the presence of a solid basic catalyst obtained by heating at 200-450oC. in the inert gas, hydride of an alkali metal and Al2O3pre-treated carbonate or alkali metal aluminate.

Slaugh (German patent 2336138) reveals the double bond isomerization of normal alkenes with 20-100oWith over a catalyst consisting of salts on activated carrier of aluminum oxide (pre-treated for 2-16 hours at 350-700oWith in a non-oxidizing atmosphere).

AVT is the PR can be applied to almost complete isomerization of alpha-olefins, linear internal olefins with a minimum formation of branched olefins. This discovery is an important achievement in the field of processing of olefins, since the catalyst comprising a Nickel deposited on a silicon dioxide/aluminum oxide is an economic alternative to the previously used catalysts and indeed more effective than known catalysts used in this reaction.

Summary of the invention In accordance with one of the technical solutions of the present invention relates to a method for applying a catalyst comprising a Nickel deposited on a silicon dioxide/aluminum oxide, with the aim of obtaining a mixture of linear internal olefins of the alpha-olefin feedstock, and this method involves the heating of raw materials in the presence of a specified catalyst.

In accordance with a preferred variant of the present invention, the temperature under heating in the above way is 100-250oC.

According to another preferred variant of the present invention stage heating in the above way is a periodic or continuous reaction.

According to another preferred variant of the present invention, the reaction mixture in casanto the present invention relates to a method of isomerization With4-C40alpha-olefins with the formation of a mixture containing at least 80 weight. % linear internal olefins, moreover, such a method comprises heating With4-C40alpha-olefins in the presence of a catalyst comprising a Nickel deposited on a silicon dioxide/aluminum oxide.

In accordance with a preferred variant of the present invention, the reaction mixture in the above method contains at least 90 wt.% linear internal olefins.

According to a more preferred variant of the present invention a mixture of the above method comprises less than 5 wt.% skeletal isomers formed under the action of a catalyst.

In accordance with another preferred variant of the present invention, the reaction mixture in the above method comprises less than 5 wt.% the residual alpha-olefins.

In another preferred solution of the present invention the stage of heating the above method is carried out at a temperature of 100-250oC.

Detailed description of the invention the Present invention provides a method of obtaining a linear, internal olefins, alpha-olefins using Nickel/aluminum catalyst.

Examples Gave the osenia way. Although the examples provided for illustration of the present invention, they do not limit its scope.

Example 1 Linear C16alpha-olefin in a flow reactor with continuous action brought in contact with 100 g of Nickel catalyst deposited on a silicon dioxide/aluminum oxide with the aim of obtaining linear internal olefins without substantial increase in the number of branched olefins. Average hourly feed rate (WHSV) of 0.9 to 1.5. The reaction temperature 100-250oC. table 1 summarizes the data obtained in a flow reactor with continuous action.

Example 2 In the periodic comparative experiments in a round bottom flask with a capacity of 250 ml of the catalyst was combined with 100 ml of C16alpha-olefin. The reaction mixture was heated to the working temperature and was stirred for a certain period of time. The results are presented below in table 2. In experiments 1-3 used the catalyst Chevron LISO, representing Nickel supported on alumina, which is described further in example 4. In experiment 4 used the catalyst STC-500 from Crosfield, which are solid Nickel on aluminum oxide. In experiment 5 was used the catalyst Ni-3288 from Engelhard, predstavliate SAPO-11.

Example 3 In a flow reactor with continuous action were contacting linear C18alpha-olefin with a catalyst comprising a Nickel deposited on a silicon dioxide/aluminum oxide, to obtain a linear internal olefins without substantial increase in the content of branched olefins. Average hourly feed rate (WHSV) was 0,72-1,52. The reaction temperature was maintained in the range of 100-250oC. table 3 summarizes the data obtained in a flow reactor with continuous action.

Example 4 Preparation of catalyst Chevron LISO, representing the Nickel deposited on a silicon dioxide/aluminum oxide
The catalyst is a promoted Nickel zeolite type pentasil with a binder of aluminum oxide. Zeolite type pentasil receive in accordance with the method of U.S. patent 3702886, "Crystalline zeolite ZSM-5 and method of preparing the same", R. Argauer and G. Landolt, issued in the name of Mobil Oil Corporation. The preferred composition is a zeolite with a molar ratio of SiO2/Al2O380-90. The zeolite was caliciviral in order to remove the organic matrix and then subjected to ion exchange with translation in the N-form (acid) using such strong Mineralien. Then the zeolite was compoundable with natroalunite powder with low content of sodium, and then formed in the extrudate, spheres, granules and tablets. A mixture consisting of 70 to 80% zeolite in dry substance (preferably 75%), and 20-30% of a powder of aluminum oxide calculated on dry substance (preferably 25%) were intensively mixed in the mixer followed by the addition of water, optionally containing 2-5% nitric acid with the aim of peptization of the alumina. The resulting mixture was then extrudible, grained, gave a spherical shape, or made into tablets using methods known to experts in this field. The preferred form is extrudate, which can be obtained by using an extruder, manufactured Bonnet Company. The extrudates were dried and illnerova at 450-550oWith decarbonization chamber, torque or conveyor type. Whether the extrudates were then impregnated with a solution of Nickel salts to produce in the finished catalyst monoxide Nickel in the amount of 1-10 weight. % of the final catalyst and illnerova at a minimum temperature of 450oC.

Using the above described method has been the catalyst with sleduyushiye when 537,8oC, %
Ni - 6,01,0
SiO2- 66,01,0
Al2O3- 26,41,0
Na, h/million -150
Fe, ppm500
Mg, h/million -500
Sa, h/million -500
The physical properties of the catalyst LISO
The shape of the Extrudate
Size - 1/16", 1/10" CDS, 1/8"
Bulk density in the compact state, lb/ft3- 423
The crushing strength, lb/mm -2,0
Surface area by BET, m2/g -275
Pore volume (Hg) cm3/g - 0,30 - 0,45
Abrasion resistance (ASTM) -2,0
Although the present invention described above with reference to specific technical embodiment, the present application encompasses various changes and modifications which may be made by the experts, without deviating from the scope and essence of the attached claims.


Claims

1. Method of isomerization of alpha-olefins to obtain a linear internal olefins, comprising heating the alpha-olefins in the presence of a catalyst zeolite, otlichayushiesya an oxide of Nickel in the amount of 1-10 weight. %.

2. The method according to p. 1, characterized in that the temperature during heating is from 100 to 250oC.

3. The method according to p. 1, characterized in that stage of heating is a periodic or a continuous process.

4. The method according to p. 1, characterized in that the mixture of the reaction products contain at least 80 weight. % linear internal olefins.

5. Method of isomerization of alpha-olefins With4-C10to obtain a linear internal olefins, comprising heating the alpha-olefins in the presence of a catalyst is a zeolite, wherein the catalyst used zeolite-ZS-5, containing the promoter isomerization representing monoxide Nickel in the amount of 1-10 weight. %.

6. The method according to p. 5, characterized in that the reaction mixture contains at least 90 weight. % linear internal olefins.

7. The method according to p. 5, characterized in that the reaction mixture contains less than 5 weight. % of skeletal isomers formed under the action of a catalyst.

8. The method according to p. 7, characterized in that the reaction mixture contains less than 5 weight. % residual alpha-olefins.

9. The method according to p. 5, characterized in that stage heating is carried out at a temperature of 100-250oWith

 

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