Method of isomerization, the isomerization product (options), composition and invert drilling muds with their use (options)

 

(57) Abstract:

Using (petrochemicals). The essence: a mixture of vinyl and vinylidene olefins having from 10 to 35 atoms ogorode, is subjected to isomerization under conditions that allow to obtain a mixture, which contains di-substituted and tri-substituted internal olefins containing deep internal olefins. Effect: improve the quality of target products. 6 N. and 15 C.p. f-crystals, 7 PL.

The invention relates to the isomerization of olefins, and more particularly, relates to the isomerization of a mixture of vinyl olefins and vinylidene (a mixture of vinyl and vinylidene olefins).

A mixture of linear terminal mono-olefins, which is usually referred to as lineinymi alpha-olefins, in industrial conditions produced by the growth of the ethylene chain Akilov aluminum, with subsequent replacement. Such products are mostly vinilovie olefins and have the following structure:

where R1represents an aliphatic hydrocarbon group. These olefins are called "vinilovie olefins". In addition, a significant portion of the alpha olefin may be in the form of "vinylidene olefins" with the following structure:

For many applications it is highly desirable to use a linear internal olefins. Linear internal olefins can be obtained from alpha-olefins by double bond isomerization of olefins from a terminal in the inner position. Such linear internal olefins may be represented by formulas 3, 4, 5 or 6.

and R1in formulas 3, 4 and 5 are determined in accordance with formula 1, a R2and R3in the formula 6 is determined in accordance with formula 2. Olefins, which have a structure according to formulae 3, 4 and 5, known as "di-substituted internal olefins. Olefins, which have a structure according to formula 6, known as the "tri-substituted internal olefins. In formulas 3 and 4 olefinic double bond is located respectively at the carbon atoms with the second and third rooms. In the formula 5 of the double bond is located at the carbon atom with the fourth number. Internal olefins in which the olefinic double bond is located at the carbon atoms with the fourth and higher numbers (for example, fifth and sixth), referred to as "deep" internal olefins.

In U.S. patent No. 4587374 shown that when used is part of olefinic groups vinylidene olefin undergoes isomerization in adjacent relationship to the carbon-carbon what are tri-substituted internal olefins. In U.S. patent No. 3864424 shown that the use of aluminum oxide or a combination of aluminum oxide with a strong acid as a catalyst for the isomerization of possible isomerization of olefinic double bond with the tertiary carbon atom in the double bond from the secondary carbon atoms, and the use of partially negidrirovannogo weak acid catalyst aluminum oxide causes isomerization of olefinic double bond with the tertiary carbon atom, with the formation of three-substituted atilano, without significant additional isomerization of 1,2-di-substituted olefins, and without the formation of dimers with other molecules with double bonds. Furthermore, in U.S. patent No. 4225419 shows that the catalysts of alumina are effective for skeletal isomerization of olefins in a more highly branched olefins.

Thus, hitherto unknown method of isomerization of alpha olefins with the formation of a product having the desirable characteristics and containing both di-and tri-substituted internal olefins, as well as having a higher degree of branching, the kinematic viscosity of less than 4 SS the morning olefins, that is, the internal olefins in which the olefinic double bond does not use the carbon atoms with the second and third rooms.

The General objective of the present invention is to provide an improved method for the isomerization of a mixture of vinyl and vinylidene olefins, which allows to obtain a product with the above-mentioned desirable characteristics.

More specifically, the present invention is to provide a method that produces the isomerization of a mixture of vinyl and vinylidene olefins to obtain a mixture, which contains both di-and tri-substituted internal olefins, and has a higher degree of branching and contains at least 20 wt.% deep internal olefins.

Another objective of the present invention is to provide an improved method for isomerization, which allows you to get the isomerization product having a viscosity of less than 4 cSt, measured at 40C., and a pour point below -25C.

These and other features of the invention will be more apparent from the subsequent detailed description and claims.

In accordance with the present invention it is proposed a method of isomerization, insidenova olefins, containing from 10 to 35 carbon atoms in the gas or liquid phase, with a layer of particles of a porous solid acid catalyst containing gamma alumina and having a specific surface area of at least 100 square meters per gram, pore volume at least 0.4 cubic centimeters per gram, an average pore diameter of at least 30 angstroms, the sodium content is less than 0.01 wt.% and the chemisorption of ammonia of at least 0.1 millimole per gram, at the reaction temperature in the range of approximately from 200C to 400C at an absolute pressure of reaction in the range of approximately from 15 to 500 psig (from 1.05 to 35 kg/cm2), and average hourly feed rate of raw materials, component of approximately from 0.5 to 20 kg olefin mixture per kg of particles of catalyst per hour, and the reaction temperature, pressure and average hourly feed rate is chosen in such a way as to form a product mixture, which contains at least 70 wt.% di - and tri-substituted internal olefins, of which in the mixture of the product contains at least 20 wt.% tri-substituted internal olefins, and at least 20 wt.% di-substituted internal olefins mixture of the product have a double bond at the carbon atom with the fourth and Bo the IDE at the carbon atom with the second and third numbers of the provisions moreover, the product has a kinematic viscosity measured at 40C, which is less than 4 Centistokes (CST), and pour point below -25C.

The present invention also relates to a product obtained by means of this method, which has a specified composition, and the base oil of the drilling fluid contains at least part of such product or such a mixture.

The source material used in the method in accordance with the present invention, is a mixture of alpha-olefins, which contains vinyl and vinylidene olefins with the structure in accordance with formulas 1 and 2, having from 10 to 35 carbon atoms. A mixture of alpha-olefins contains, and mainly consists primarily of olefins which have from 16 to 18 carbon atoms. Despite the fact that such a mixture can be obtained in various ways, appropriate industrial mode of production is the process Ziegler, in accordance with which the provide chain growth triethyl aluminum-ethylene with further substitution. The obtained olefin mixture typically contains approximately 50 to 95 wt.% vinyl olefins in accordance with formula 1 and approximately 5 to 50 wt.% waste raw material for carrying out the method in accordance with the present invention, contain approximately 60 to 90 wt.% vinyl olefins in accordance with formula 1 and approximately 10 to 40 wt.% vinylidene olefins in accordance with formula 2.

In the above formulas 1, 3, 4 and 5, R1may contain from 5 to 30 carbon atoms, and predominantly from 11 to 13 carbon atoms. Examples of such vinyl olefins are 1-mission 1-dodecene, 1-tetradecene, 1-hexadecene, 1 octadecene, 1-eicosan, etc., In accordance with the most preferred option, vinyl olefins in the mixture mainly contain 1-hexadecene and 1 octadecan.

In formulas 2 and 6, each of R2and R3contains from 1 to 29 carbon atoms, and their sum is from 5 to 30 carbon atoms, and predominantly from 11 to 13 carbon atoms.

In addition, the original olefinic mixture prior to the isomerization according to the method in accordance with the present invention may contain internal olefins. Generally, the amount of internal olefins in the mixture is relatively low and typically is in the range from 0 to 15 wt.%. Generally, the amount of internal olefins is about 3-10 wt.% the initial mixture, of which very little or no tri-substituted olefins. Needless Rasulev in raw materials for isomerization is not a critical constraint.

Table 1 shows typical olefin mixtures which can be used as raw material for the method of isomerization in accordance with the present invention.

When implementing the method in accordance with the present invention is injected into contact with raw materials that are in the gas or liquid phase, with a layer of particles of a porous solid acid catalyst containing gamma alumina. Mainly the catalyst particles contain at least 95 wt.%, and even better, at least to 99.5 wt.%, gamma alumina. Most preferably, if the catalyst particles consist mainly of gamma alumina. The gamma alumina has a specific surface constituting at least 100 square meters per gram, and mostly at least 150 square meters per gram, pore volume at least 0.4 cubic centimeters per gram, and most at least of 0.5 cubic centimeters per gram and an average pore diameter of at least 30 angstroms, and mostly at least 40 angstroms. In addition, gamma aluminum oxide, the sodium content is less than 0.01 wt.% and the chemisorption of ammonia, comprising at least 0.1 millimole per gram.

The choice of temperature and pressure of reaction, as well as average hourly feed rate of raw materials, these ranges are produced so that the product mixture resulting from the application of the method in accordance with the present invention, had the following composition, as well as below the freezing temperature and kinematic viscosity. More specifically, obtained using the method of isomerization in accordance with the present invention the product is a combination product that contains di - and tri-substituted internal olefins. Less than 50 wt.%, and mostly less than 40 wt.% internal olefins in the above-mentioned mixture of the product have a double bond at the carbon atom in the second and third position in the formula 3 or 4. At least 20 wt.%, but mainly at IU is ogenyi (formula 5) or in a higher position, such olefins are called "deep" olefins. At least 20 wt.%, and mostly at least 25 wt.% internal olefins in the above-mentioned mixture of the product represent a three-substituted internal olefins according to formula 6. The sum of the concentration of internal olefins with the double bond of the carbon atom in the third position (formula 4) plus the concentration of "deep" olefin is preferably at least 45 wt.%, and even better, at least 50 wt.%. Obtained by the method in accordance with the present invention, the product has a kinematic viscosity of less than 4 cSt, and mostly less than 3.5 cSt, measured at 40C., and a pour point of lower than -25C and mostly lower than 27C, and even better lower than -30C.

In addition, to obtain the specified product with the desired chemical composition and the desired properties of the mixture of the product obtained by the method in accordance with the present invention, it is desirable to limit the occurrence of side reactions dimerization and cracking. Formed in the isomerization product of the cracking has 14 or fewer carbon atoms. Thus, a mixture of the product obtained by the method in accordance with the form of the olefin in the feedstock, and less than 10 wt.%, and mostly less than 5 wt.% product of the cracking of the olefins in the feedstock.

In accordance with another aspect of the present invention olefinic composition obtained by the method in accordance with the present invention, contains at least 70 wt.% di - and tri-replaced internal olefins having from 10, and predominantly from 16 to 35, and even better, to 18 carbon atoms. At least 20 wt.%, and mostly at least 25 wt.% such a composition in accordance with the present invention are three-replaced internal olefins according to formula 6. Less than 50 wt.%, and mostly less than 40 wt.% internal olefins in the composition in accordance with the present invention have a double bond at the carbon atom in position 2 (formula 3) or 3 (formula 4). At least 20 wt.%, and mostly at least 25 wt.% internal olefins have a double bond at the carbon atom in position 4 (formula 5) or at the carbon atom in the higher position. The sum of the concentration of internal olefins with the double bond of the carbon atom in the third position (formula 4) plus the concentration of "deep" olefin is preferably at least 45 wt.%, and even better, be less than -25C, and mostly less than -30C., and a viscosity, measured at 40C, which is less than 4 CST, and mostly less than 3.5 CST.

Parameters that are important for the selection of base oils intended for use in the compositions of the drilling fluid, are the kinematic viscosity, for example, at 40C, and pour point. Obtained by the method in accordance with the present invention the product has such kinematic viscosity and pour point, which you can use it as a base oil (or the main part of it) for invert drilling mud. Usually invert drilling muds contain at least 50 vol.%, but mainly it is estimated that between 65 to 95 vol.% base oil as the continuous phase, approximately up to 50 vol.%, but mainly it is estimated that between 5 to 35 vol.% water (which contains approximately 38 wt.%, but mainly it is estimated that between 20 to 35 wt.% sodium chloride or calcium), as well as conventional drilling additives, such as emulsifiers, thickeners, controls, alkalinity, controls, filtration, water-repellent agents (humectants oil) and data loss prevention solution (fluid orientirovochno at least 75 vol.% the base oil consists of a product by the method in accordance with the present invention (or compositions in accordance with the present invention).

Water in oil emulsion is formed due to intensive mixing the base oil with one or more emulsifiers. There are various suitable emulsifiers, including Soaps of fatty acids, mainly calcium soap, polyamides, sulfonates, triglycerides, etc. Soaps of fatty acids can be formed at the location by adding desirable fatty acids and bases, mostly lime. Emulsifiers are generally used in amounts of from approximately 1 to 8 kg per cubic meter of drilling fluid.

Drilling muds also contain, which is in itself known, one or more additives, such as thickeners, weights, water-repellents and means preventing absorption (loss) of the drilling fluid, which allow to take into account the specific requirements of the drilling operations. Supplements help to support drilling cuttings and waste in suspension, provide the desired viscosity, density and additional wetting solution, and prevent the loss of liquids from a solution due to the migration of fluids in the formations surrounding the borehole.

Mud using clay and polymeric thickeners, such as bentonite and Eulogy, starches and gums in quantities of approximately from 0.5 to 5 kg per cubic meter of drilling fluid.

The density of the drilling fluid can be increased through the use of weights, such as bartik (bartic), Galena, iron oxides, siderite, etc., upon receipt of the densities in the range from approximately 950 to 2400 kg per cubic meter of drilling fluid.

To facilitate the retention of the solid additives in suspension in the drilling fluid can be introduced repellent agents, such as lecithin or organic esters poliedriceskaa alcohols, in the amount of approximately up to 4 kg per cubic meter of drilling fluid.

Can be used fluid filter (means of loss prevention solution), such as organohalide humates derived from the reaction of humic acid with inorganic salts polyalkylene polyamines, which cover the walls of the well, and they are used in amounts approximately to 7 kg per cubic meter of drilling fluid.

Invert drilling mud, which is formed using the product obtained in the form of base oils in the following explanatory Example 2 has the following composition:

213,5 grams of the product will explain the mul,

2 grams of wetting agent and surfactant type Novawet,

6 grams of lime,

94,9 grams of brine 25% of calcium chloride,

162,19 grams of barite.

Was prepared drilling mud by adding the above ingredients in the order listed. Thickener VG-69 is organogenous clay-based bentonite. Emulsifier Novamul is a mixture of different emulsifiers, humectants, ogilivy agents and stabilizers solution, in which you want to add lime, creating a calcium soap. This emulsifier is a primary additive in "normal" invert systems mud.

Table 2 shows the parameters of the product in accordance with the following explanatory Example 2 and characteristics containing this product mud. The curing solution is carried out for 16 hours at 122C in a hot drum furnace. Gel strength is shown for 10 seconds and 10 minutes, for example, 6/7 for 10 seconds and 10 minutes. The received drilling fluid was subjected to testing for 96 hours in accordance with the test line with an50on short-term toxic effects on the shrimp mysid shrimp.

skretny examples. In each of the explanatory Examples 1-23 and comparative Examples 1-3, the source material is a mixture of approximately 55 wt.% 1-hexadecene and approximately 45 wt.% 1 octadecene, and approximately 1 wt.% p-hexadecane and n-octadecane. The source material contains 63,98% wt. vinyl olefin and 28,99% wt. vinylidene olefins.

Illustrative examples 1-23

In each of the explanatory Examples 1-23 in the tubular reactor was loaded catalyst of gamma alumina type Engelhard's AL-3996-CR. The specified catalyst has the following characteristics:

Specific surface 217 m2/year

Pore volume is 0.65 cm3/year

The average pore diameter of 43 angstroms.

Sodium - 0,0074%.

Chemisorption of ammonia - 0.1 millimole per gram.

In each of Examples 1-8 was used 450 grams of catalyst were loaded into a tubular reactor with an inner diameter of 2 inches (5 cm). The catalyst was used without pre-treatment, and the source material has come in contact with the catalyst at an average hourly feed rate of raw materials 1.7 kg of raw material per kg of catalyst per hour. In each of Examples 9-23 used 10 grams of catalyst C is Isadora by purging with nitrogen at a temperature of 450C for 16 hours. Table 3 shows the used reaction temperature, the measured pressure and average hourly feed rate of raw materials, as well as the turnover of the catalyst. Table 3 also shows the initial and final concentration of vinyl olefins in the reaction mixture and the mixture of the product and the freezing temperature of the reaction mixture and the mixture product.

Detailed composition of the raw material used and the product mixtures obtained in Examples 2 and 9, are shown in Table 4.

COMPARATIVE EXAMPLES

Comparative example 1. Five grams of catalyst type Engelhard X-353 (phosphorus molybdenum acid on titanium oxide, 18/40 mesh) were loaded into a tubular reactor (internal diameter 1 inch (2.5 cm), then made the purging with nitrogen at a temperature of 196C for 20 hours. Thereafter, the catalyst was cooled to room temperature and brought into contact with the catalyst raw materials at an average hourly rate of feed 10 grams of raw material per gram of catalyst per hour. Then the temperature of the contents of the reactor was raised to 125C. the results are shown in Table 5 and show that the catalyst was mostly completely not active.

Comparative example 2. Five grams to the) diameter 1 inch (2.5 cm), then made a pre-treatment in nitrogen at a temperature of 150C for 4 hours. After that, the reactor was cooled to room temperature and brought into contact with the catalyst raw materials at an average hourly rate of feed 10 grams of raw material per gram of catalyst per hour. Then the temperature of the contents of the reactor was raised to 125C. the results are shown in Table 6 and show that the catalyst also was mostly completely not active.

Comparative example 3. Five grams of the catalyst of gamma alumina (Engelhard A1-3996-CR) were loaded into a tubular reactor (internal diameter 1 inch (2.5 cm), then made a pre-treatment in nitrogen at a temperature of 150C for 18 hours. After that, the reactor was cooled to room temperature and brought into contact with the catalyst raw materials at an average hourly rate of feed 10 grams of raw material per gram of catalyst per hour. Then the temperature of the contents of the reactor was raised to 125C. After that, to improve the activity of the catalyst, the temperature was raised to 180C and reduced the average hourly feed rate is approximately 5. The results are shown in Table 7 and show that the catalyst also in the embodiments of the invention, it is quite clear that they are presented only to illustrate the present invention and that they are specialists in this field may be amended and supplemented, which do not extend, however, beyond the scope of the following claims.

1. Method of isomerization of linear alpha olefin mixture containing vinyl and vinylidene olefins having 10 to 35 carbon atoms, characterized in that it comprises the following operations: introduction to contact alpha olefin mixture in the gas or liquid phase, with a layer of particles of a porous solid acid catalyst containing gamma alumina and having a specific surface area of at least 100 m2/g, pore volume of at least 0.4 cm3/g, an average pore diameter of at least 30 , the sodium content is less than 0.01 wt.% and the chemisorption of ammonia of at least 0.1 mmol/g, at the reaction temperature in the range of approximately from 200 to 400°C at an absolute pressure of reaction in the range of approximately from 1.05 to 35 kg/cm2at an average hourly feed rate of raw materials, component of approximately from 0.5 to 20 kg olefin mixture per kg of particles of catalyst per hour, and the reaction temperature, pressure and average speed SOPs - and tri-substituted internal olefins, of which in the mixture of the product contains at least 20 wt.% tri-substituted internal olefins, and at least 20 wt.% di-substituted internal olefins mixture of the product have a double bond at the carbon atom with the fourth and higher numbers of positions, while less than 50 wt.% di-substituted internal olefins have a double bond at the carbon atom with the second and third numbers of provisions, and the product has a kinematic viscosity measured at 40°C, component of less than 4 cSt, and a pour point below -25°C.

2. The method according to p. 1, wherein the alpha olefin mixture consists primarily of olefins which contain from 16 to 18 carbon atoms.

3. The method according to p. 1, characterized in that the product mixture contains at least 80 wt.% di - or tri-substituted internal olefins.

4. The method according to p. 1, wherein at least 25 wt.% received internal olefins are di-substituted internal olefins having a double bond at the carbon atom in the fourth or a higher position.

5. The method according to p. 1, characterized in that less than 40 wt.% received internal olefins are di-substituted internal aleisa fact, the product mixture contains at least 25 wt.% tri-substituted internal olefins.

7. The method according to p. 1, characterized in that at least 45 wt.% received internal olefins represent the sum of the internal olefins having a double bond at the carbon atom in the third position, and internal olefins having a double bond in the fourth or a higher position.

8. The method according to p. 1, characterized in that the mixture of the product has a pour point lower than approximately -30°C.

9. The method according to p. 1, characterized in that the mixture of the product has a kinematic viscosity measured at a temperature of 40°C, component approximately less than 3.5 cSt.

10. The method according to p. 1, characterized in that the particles of the solid catalyst has pores with an average diameter constituting at least 40 .

11. The method according to p. 1, characterized in that the particles of the solid catalyst contain at least 99,5% wt. gamma alumina.

12. The method according to p. 11, characterized in that the particles of the solid catalyst contain at least a 99.0 wt.% gamma alumina.

13. The method according to p. 1, characterized in that the reaction temperature is in the range orientirovochno range approximately from 1 to 15 kg olefin mixture per kg of catalyst particles per hour.

15. The product obtained by the method according to p. 1.

16. The product obtained by the method according to p. 2.

17. Invert drilling fluid, characterized in that it contains at least about 50 vol.% base oil containing at least about 25 vol.% the product obtained by the method according to p. 1.

18. Invert drilling mud under item 17, characterized in that at least about 25 vol.% base oil is the product obtained by the method according to p. 2.

19. Composition for use in drilling fluids, characterized in that it is an olefin mixture having from 10 to 35 carbon atoms and containing at least 70 wt.% di - or tri-substituted internal olefins, and at least 20 wt.% the specified composition to form a three-substituted internal olefins, and at least 20 wt.% olefins specified compositions have a double bond at the carbon atom in the fourth or a higher position, and less than 50 wt.% olefins specified compositions have a double bond at the carbon atom in the second or third position, the said mixture has a kinematic viscosity measured at a temperature of 40°C, component of less than 4 cSt, and a pour point below -25&#which have 16 to 18 carbon atoms.

21. Invert drilling fluid, characterized in that it contains at least about 50 vol.% base oil containing at least about 25 vol.% songs by p. 19.



 

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