The method of receiving agent reducing the hydrodynamic resistance of hydrocarbon liquids

 

(57) Abstract:

Agent reducing the hydrodynamic resistance is (co)polymerization of alpha-olefins with the number of carbon atoms from 4 to 14 on highly active titanium-magnesium catalyst deposited on a magnesium chloride-titanium tetrachloride, and socializaton alyuminiiorganicheskikh connection at (-30) - 50oSince, in the presence of catalytic modifier system - silicone compound. Used for transportation of hydrocarbon fluids. Effect: reduction of the time of polymerization, reduction of compounds of titanium, the increase of the characteristic viscosity (co)polymer, a product with a good yield and with good solubility in hydrocarbons. 5 C.p. f-crystals, 1 table.

The invention relates to methods of producing polymers of olefins, effectively reducing the hydrodynamic resistance of hydrocarbon liquids and can be used for transporting petroleum products in pipelines.

The use of these polymers in pipeline transportation of oil and oil products allows you to save pumping energy consumption or to increase the capacity Truboprovod: well soluble in hydrocarbon fluids, i.e. to have a certain level of stereospecificity, and to have a sufficiently high molecular weight. However, the greater the molecular weight, the lower the concentration of polymer in the fluid flow needed to reduce hydrodynamic resistance.

It is known that olefins can be polymerized in the presence of catalysts of the Ziegler-Natta. These catalysts usually contain components such as titanium halides and ORGANOMETALLIC socializaton, such as aluminiumgie or aluminiumbyggande.

An important feature of the polymerization of higher a-olefins is that to achieve a sufficiently high molecular weight requires a relatively low temperature, of the order of (-30)- (+10)oC. However, by increasing the viscosity of polymerizate decreases the rate of polymerization, which is undesirable in industrial production. To increase the rate of reaction at low temperatures using various adjuvants, as a rule, electron-donor character.

To obtain crosslinked and non-crystalline poly-olefin with good solubility in hydrocarbons, suitable for skin is La catalytic system TiCl31/3AlCl3(company "Stauffer Chemical Co") proposed to use compounds selected from the group of ester or carbonyl compounds (U.S. Pat. USA N 4415714, MKI C 08 F 4/64, Appl. 29.01.81, publ. 15.10.83) or organic phosphines or phosphites (U.S. Pat. USA N 4433123, MKI C 08 F 4/64, Appl. 12.05.81, publ. 21.02.84). According to the patent polymerization cut by 20% the stage of conversion to increase the average molecular weight of the product. However, high consumption of the monomer and the catalyst to obtain a polymer with a low characteristic viscosity [] 11,1 make this method uneconomical.

Also as an activator in the polymerization at low temperatures using polysiloxane (U.S. Pat. USA N 5028574, MKI C 08 F 4/649, publ. 02.07.91, Appl. 14.03.90). However, when receiving poly-mission at 0oC the characteristic viscosity [] about 12 DL/g, the process goes within 24 hours, which is the main disadvantage of this method.

To reduce the time of polymerization of higher a-olefins in the system, including aluminothermic catalyst TiCl31/3AlCl3company "Stauffer Chemical Co. proposed to add to it as the activating agent connection type alkoxyamine (U.S. Pat. USA N 4845178, Mcisb, at a relatively low characteristic viscosity of 9.8 DL/g and the polymer yield is 7.4%.

The known method of polymerization of C4-C40alpha-olefins (U.S. Pat. EP N 627449, MKI C 08 F 10/08, Appl. 25.05.94, publ. 07.12.94) with the use of highly active titanium-magnesium catalyst (TMK) supported on magnesium chloride of titanium tetrachloride. However, the resulting products are not the subject of this invention, in particular the molecular weight of the obtained polydecene-1 did not exceed 204000, which corresponds to a characteristic viscosity in tetrahydrofuran approximately 3.7 DL/g

The closest in technical essence and the achieved result is a method for agents of reducing the hydrodynamic resistance polymerization of higher a-olefins in the environment of the hydrocarbon solvent using a catalytic system consisting of the product of the reduction of titanium tetrachloride alyuminiiorganicheskikh connection and alyuminiiorganicheskikh of socializaton on certain relationships with the monomer at a temperature of (-30)-(+20)oC for a considerable amount of time 5-7 hours (U.S. Pat. RF N 2075485, MKI C 08 F 10/14, Appl. 10.03.94, publ. 20.03.97).

The disadvantages of the method are a big rashei of the invention is to reduce the time of polymerization, reduction of compounds of titanium, the increase of the characteristic viscosity (co)polymer, a product with a good yield and with good solubility in hydrocarbons.

The problem is solved in that in the present method (co)polymerization individual C6-C12-olefins or a mixture of two or more C4-C14-olefins, the content of each monomer is not less than 10 mol%, carried out in a medium of hydrocarbon solvent in the presence of a highly active catalyst of titanium tetrachloride supported on magnesium chloride, activated trialkylaluminium when the ratio of olefin : catalyst (calculated as Ti) : trialkylaluminium equal 0,4 - 1,0 : 0,000005-0,00005: 0,0005-0,01. The process is carried out at the initial concentration of monomer in solution 30 - 99% and in the temperature range from -30oC to +50oC. When the polymerization may optionally be entered organosilicon compound of General formula RmSi(OR')nwhere m = 1 or 2, n = 2 or 3, R is alkyl or aryl, R' is alkyl (C1-3a molar ratio of aluminum: silicon is 1:0.1 to 10. As alyuminiiorganicheskikh of socializaton use tea or CHIBA.

As organosilicon compounds can ELA can be used heptane, nefras or kerosene and other paraffin hydrocarbons.

When comparing essential features of the invention revealed that the characteristics:

- the use of highly active titanium-magnesium catalyst to obtain amorphous ultra-high molecular weight (co)polymers C4-C14-olefins in the specified proportions of monomer, catalyst, socializaton,

- (co)polymerization at a temperature of (-30)-50oC, initiating the polymerization at a temperature of not more than 20oC,

- use as alyuminiiorganicheskikh of socializaton of triethylaluminum or triisobutylaluminum,

- additional introduction of organosilicon compounds in the ratio indicated,

- use-olefins C4-C14with concentration in the solution is equal to 30-99%,

- the use of (co)polymers of olefins, C4-C14as agents of reducing the hydrodynamic resistance,

are new and are not described in the prototype, so you can make a conclusion about conformity of the proposed technical solution the criterion of "novelty".

The inventive method allows to obtain ultra-high molecular weight (co)polymers in a wide range of temperatures, with good the stroke of the polymer and the characteristic viscosity of the resulting product, to reduce the hydrodynamic resistance of the diesel fuel, which cannot be done by any equivalent means, and indicating "inventive step" of the proposed method.

Set ratios of the reactants are chosen experimentally and are optimal: lower limits are determined by the possibility of reaction (co)polymerization with the formation of ultra-high molecular weight (co)polymer; the upper limits of the optimal viscosity of the solution obtained (co)polymer that provides effective heat and mass transfer.

The method was carried out as follows. In the reactor in a stream of dry nitrogen was loaded hydrocarbon solvent (heptane, nefras or kerosene), the estimated amount of solution trialkylamine (and possibly organosilicon). After stirring was added a suspension of deposited titanium-magnesium catalyst and the resulting solution of catalyst complex was placed in a water bath. When establishing the desired solution temperature initiated (co)polymerization of the addition-olefin. As thickening of the solution, during the (co)polymerization temperature of the reaction mixture can spontaneously rise up to 50oC, the reaction of (co)polymerization was stopped by the addition of alcohol, for example ethyl. The reaction mass was wizardly acetone obtained (co)polymer was dried to constant weight.

The characteristic viscosity of the resulting (co)polymers was determined in a solution of tetrahydrofuran at a temperature of 20oC GOST 33-82.

Output (co)polymer considered per unit mass of catalyst (in terms of titanium) per unit time according to the formula

< / BR>
where MPthe mass of the obtained (co)polymer (g), MC- weight of catalyst (calculated as titanium) (g), the time of polymerization, (h).

Hydrodynamic testing agents reducing the hydrodynamic resistance was performed on circulation installation with pipe length of 16 m and a diameter of 20 mm using diesel fuel as the test product. The concentration of the agent reducing the hydrodynamic resistance was 10 ppm. Reducing hydrodynamic resistance was determined by the formula

< / BR>
where P is the pressure drop in the pipeline for diesel fuel, Pp- pressure drop in the pipeline after the addition (co)polymer; Q and Qpthe flow in the pipe for untreated and diesel fuel, respectively.

Results Il, ,001 M of triethylaluminum. The mixture was stirred and added 0.04 g of paste of titanium-magnesium catalyst (Ti content 0,000005 M). The resulting solution of catalyst complex was cooled in a water bath with stirring until a temperature of the solution 0oC. the Polymerization was initiated by adding 0.4 M (50 ml) of 1-hexene and 3 hours interrupted the reaction by adding 20 ml of ethyl alcohol. The reaction mass was wizardly acetone, the polymer was dried to constant weight. The polymer yield - 10040 g/g Ti h, characteristic viscosity [] = 13,1 DL/g

Example 2. In the reactor in a stream of dry nitrogen was downloaded 117 ml of heptane, 0.001 M of triethylaluminum and 0.00005 M n-propyl-trimethoxysilane. The mixture was stirred and added 0.04 g of paste of titanium-magnesium catalyst (Ti content 0,000005 M). The resulting solution of catalyst complex was cooled in a water bath with stirring until a temperature of the solution 0oC. the Polymerization was initiated by adding 0.4 M (50 ml) of 1-hexene, and further processed as described in example 1. The polymer yield 9080 g/g Ti h, characteristic viscosity [] = 14,8 DL/g

Example 3 - 6, 9, 11, 12. The receiving agents of reducing the hydrodynamic resistance of hydrocarbon liquids at different sootnoshenia examples 1-2. The results are presented in the table.

Example 7. In the reactor in a stream of dry nitrogen was loaded with 50 ml of heptane, 0.01 M of triethylaluminum and 0.005 M n-propyl-trimethoxysilane. The mixture was stirred and added 0.04 g of paste of titanium-magnesium catalyst (Ti content 0,00005 M). The resulting solution was stirred at a temperature of 20oC and initiated polymerization by the addition of 0.6 M (75 ml) of 1-hexene. As the gelled solution of the possibility of heat removal is reduced. The temperature of the reaction mass begins to rise and reaches 50oC one hour after the beginning of polymerization. The reaction was stopped by adding 100 ml of a mixture of 20% vol. alcohol in heptane and further processed as described above. The polymer yield 8810 g/g Ti h, characteristic viscosity [] = 12,3 DL/g

Example 8. The copolymerization and the selection of the product was carried out as in example 2, using as monomer fraction C8-C10-olefin content of octene - 1 and mission-1 in a mass ratio of 1 : 1. The results are presented in the table.

Example 10. The copolymerization and the selection of the product was carried out as in example 1, using as (co)monomers, a mixture of butene-1, hexene-1 and tetradecene-1 in a ratio of 10 : 80 : 10 mol%.

Very high activity catalysis is azannyh above - olefins at low temperatures (up to -30oC) with reasonable speed and good output. Increased activity of the used catalyst provides a high output (co)polymer), eliminating the need to clean it from residues of the catalyst, which leads to a significant simplification of the process.

The use of individual alpha - olefins with the number of carbon atoms is less than 6 or more than 12 leads to the formation of crystalline homopolymers, sparingly soluble in hydrocarbon solvents (precipitation upon standing in solution of heptane and kerosene) and having a lower characteristic viscosity. Therefore, when using alpha-olefins of C4or C14it is desirable to use them in a mixture with one or more of the above alpha-olefins to obtain an amorphous copolymers.

As activator use the organosilicon compound of General formula RmSi(OR')nwhere m = 1 or 2, n = 2 or 3, R is alkyl or aryl, R' is alkyl (C2-3. Application of the above organosilicon compounds leads to an increase of the characteristic viscosity of the polymer and to improve anti-turbulent properties of the polymer ceteris paribus.

As the view is in the temperature range from -3oC to +50oC with the release of the polymer 7700-12100 g/g Ti h, having a good solubility in heptane, nerase, kerosene and diesel fuel, with the characteristic viscosity of the obtained product 12,3 - 21,8 DL/g, reducing the hydrodynamic resistance of the diesel fuel 21.6 - 42,8% at a concentration of 10 ppm polymer.

1. The method of receiving agent reducing the hydrodynamic resistance of hydrocarbon liquids (co)polymerization of higher a-olefins in the environment of the hydrocarbon solvent in the presence of a titanium containing catalyst and alyuminiiorganicheskikh of socializaton, characterized in that as the highest-olefins using individual-olefins from C6to C12or a mixture of two or more olefins C4-C14with the content of each monomer is not less than 10 mol. % titanium containing catalyst - deposited titanium-magnesium catalyst in the following molar ratio of reagents:

-Olefins, C6-C12or a mixture of C4-C14-olefins - 0,4 - 1,0

The catalyst (in terms of Ti) - 0,000005 - 0,00005

Alyuminiiorganicheskikh socialization - 0,0005 - 0,01

2. The method according to p. 1, characterized in that the (co)polymerization is carried out at a temperature of (-30) - 50oC, with different themes, as alyuminiiorganicheskikh of socializaton use triethylaluminium or triisobutylaluminum.

4. The method according to p. 1, characterized in that it further introduces the organosilicon compound of General formula RmSi(OR')nwhere m = 1 or 2, n = 2 or 3, R is alkyl or aryl, R' is alkyl (C1-3when the molar sootnoshenii aluminum : silicon is 1 : 0.1 to 10.

5. The method according to p. 1, characterized in that the initial concentration of olefins, C4-C14in the solution is 30 to 99 vol.%.

 

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