The method of decontamination of a complex organometallic catalyst homogeneous processes, such as dimerization or oligomerization of ethylene to linear alpha-olefins, and its separation from the reaction mass

 

(57) Abstract:

The invention can find application in the chemical and petrochemical industries, factories for the production of butene-1, linear alpha-olefins WITH4- C30(LAO) and other soluble in the reaction medium products using comprehensive ORGANOMETALLIC catalysts (KMK). The method includes decontamination KMC di - or oligomerization of ethylene in LAO by mixing the effluent from the reactor the reaction mixture containing the solvent, LAO and "live" the catalyst with a solution of the hydroxide of the metal in protonotaries a solvent such as water, alcohol or ammonia, at 60-80oand the pressure of ethylene 2-4 MPa at an additional intensification of mixing irradiation of a mixture received by the ultrasound, the allocation protonotaries solvent from the reaction mass by distillation and returning it to recycling; subsequent separation of the reaction mixture into fractions and the selection of the deactivated catalyst in conjunction with waxy LAO from the last separation columns in the form of VAT residue; the selection of the deactivated catalyst from VAT residue by extraction waxy LAO hydrocarbon solvent, inertial-totemperature oxidative mineralization highlighted the deactivated catalyst; selection waxy LAO from an extract containing hydrocarbon solvent and waxy LAO, by distillation of the hydrocarbon solvent, which also return in recycling. The technical effect of this invention is to increase the purity of the LAO, i.e., to increase the selectivity of the catalyst and process of the di - or oligomerization of ethylene. 10 C.p. f-crystals, 3 tab., 3 Il.

The invention relates to a method of decontamination of a complex ORGANOMETALLIC catalyst (KMK) of homogeneous processes, such as dimerization or oligomerization of ethylene to linear alpha olefins (LAO), and its separation from the reaction mass.

The invention can find application in chemical and petrochemical plants, which are homogeneous processes with the use of KMC in particular on plants for the production of butene-1 or LAO.

The product of the dimerization of ethylene - butene-1 is used as a source of raw material for crystalline polybutene-1, ethylene-butenova and propylene-butenova plastics (including linear low density polyethylene and elastomers, oligopotent oils, mutilations hydrocarbons, butadiene, alpha-butene oxide, alpha"ptx2">

The products of the oligomerization of ethylene - LAO C4- C30- used as a source of raw materials for the production of household cleaning products, flotation agents, emulsifiers, components, cutting and drilling fluids, plasticizers, various types of additives, synthetic waxy oils, polymers and copolymers of the monomers, of depreciation oil and oil products, higher alkylamines followed, higher alkalinemanganese compounds, coolants, synthetic fatty alcohols and acids, as well as upon receipt of components of different compositions based on LAO (C20-C30) - mastics, sealants, coatings.

In the descriptions of U.S. patents 3879485, 3911942, 3969429, UK 1447811, 1447812 and Germany 2274583, 2462771 described method of dimerization of ethylene to butene-1 in the KMC, including tetrabutoxide titanium and triethylaluminium in the environment of an organic solvent (hexane, heptane, gasoline, benzene, toluene, ethyl chloride, ethers - diethyl, dibutylamino, isopropyl, methyl isoamyl, metilfenidato, tetrahydrofuran and mixtures thereof) at temperatures of 20 to 80oC and pressures of ethylene, from 0.1 to 1.6 MPa.

In accordance with descriptions of the inventions copyright SUB> - C30carried out in a medium of an organic solvent at temperatures of 60 - 80oC and pressures of ethylene 2,0 - 4,0 MPa. As reaction medium (organic solvent) for the oligomerization of ethylene using toluene, benzene or heptane.

The oligomerization of ethylene in LAO in accordance with the specified security documents carried out under the action of KMC, which includes a zirconium salt of an organic acid - ClmZr(OCOR)4-mor ClmZr(OSO3R')4-mand alyuminiiorganicheskikh connection (AOC)-(C2H5)nAlCl3-nwhere R and R' is alkyl, alkene or phenyl; m is smoothly changed from 1 to 4; n is smoothly changed from 1 to 2.

In optimal conditions, the processes of di - and oligomerization of ethylene from beginning to end flow homophase: precipitation of the catalyst in such processes is not formed, and the soluble products of the conversion of ethylene (in particular polyethylene) formed in small quantities.

When carrying out processes of di - and oligomerization reactor for the continuous mixing of the reaction mass at the outlet of the reactor is a mixture of the solvent with the products of conversion of ethylene - butene-1 and LAO, respectively, in Kotor and products of their spontaneous thermal decontamination.

As a result of leaking di - or oligomerization of ethylene under the action of active living centres outside of the reactor in uncontrolled conditions (and in some cases due to throttling) the ethylene concentration decreases significantly increased (or reduced by throttling) temperature and dramatically increases the relative concentration of butene-1 or LAO, respectively.

The presence of active living centres, di - or oligomerization of ethylene, low concentration or absence of ethylene and relatively high (up to 8 mol/l) concentration of butene-1 or LAO in the solution determine the occurrence of secondary reactions of butene-1 or LAO: in particular, in these conditions is the isomerization of butene-1, CIS - and TRANS butenes-2; other LAO isomerized in the olefins with the double bond between intramolecular carbon atoms; simultaneously, butene-1 or LAO di-, tri - and oligomerized; become isoolefine.

Especially critical was the duration of contact of oligomerizate containing LAO live a catalyst for oligomerization of ethylene in the absence of ethylene. From table. 1 shows that in the absence of ethylene LAO R-CH=CH2under the action of catalyst oligomerizes and prevrashalis is the total concentration of double bonds in the reaction mass (table. 1) and the formation of oily oligomers with srednetsenovoj molecular weight of 350 - 800. Depth conversion of olefins with vinyl double bonds increases with the contact duration LAO with a live catalyst.

The above-mentioned catalysts for oligomerization of ethylene in LAO contain AOC (C2H5)nAlCl3-nthat are strong Lewis acids. On their basis in these systems are easily formed cationic active centers. Under the action of cationic active centers LAO also isomerized, di-, tri - and oligomerized; alkylate aromatic solvent.

It is observed that the diffusion flow in the reaction mass containing the LAO and "live" the catalyst, the concentration of water or alcohols leads to a dramatic acceleration of cationic processes and strong heating of the reaction mass. In static conditions, the diffusion processes of water and alcohols, cationic reaction LAO and heating of the reaction mass flow in the frontal mode.

All these secondary reaction of butene-1 or LAO proceed with high speed.

Favorable conditions for the occurrence of secondary reactions of butene-1 or LAO under the action live catalyste from the reaction mixture of butene-1 or narrow fractions LAO.

The occurrence of secondary reactions of butene-1 or LAO leads to the expenditure of olefins with vinyl double bonds and to the pollution of butene-1 or LAO products of their transformations. To a greater or lesser extent, this reduces the selectivity of the catalyst and process.

It is obvious that the secondary reaction of butene-1 or LAO undesirable.

To prevent the occurrence of secondary reactions of butene-1 or LAO "live" catalyst di - or oligomerization of ethylene immediately after taking out from the reactor must be decontaminated. During this period of time between the removal of the "living" of the catalyst from the reactor and its decontamination should be minimized.

Known (U.S. Pat. USA 4486615, Pat. Germany 4338415) methods of deactivation of the catalyst for the oligomerization of ethylene in LAO, including ClmZr(Osoite3H7)4-mand (C2H5)nAlCl3-n, additives stoichiometric amounts of carboxylic acids.

The drawback of the method according to U.S. Pat. USA 4486615 is the fact that as a result of deactivation of the catalyst for oligomerization of ethylene to produce large amounts of hydrogen chloride, which causes intense corrosion of the equipment.

Other nedostatkah in the allocation of the deactivated catalyst by the method of countercurrent water wash oligomerizate.

Zirconium and aluminium-containing products deactivated carboxylic acids of the catalyst according to the second method (U.S. Pat. Germany 4338415) is extracted from the reaction mixture by passing it through a bed of adsorbent with a large specific surface area. As adsorbents in this way use granular silica gel, kaolin, zeolites, alumina, Zirconia, sawdust.

The disadvantage of this method is that the deactivation of the specified catalyst alcohols leads to the formation of significant quantities of hydrogen chloride, which is not captured by the adsorbent falls into columns for the separation of oligomerizate on a narrow faction and causes corrosion.

Another disadvantage of the considered known method is the large number of chemically contaminated water runoff generated at the stage of regeneration of the adsorbents.

Another drawback to consider the well-known way of separating the deactivated catalyst is a highly complex technological design of this stage of the process, as well as difficulties in the selection of materials for the manufacture of adsorbents which are exposed in the process of regeneration of the adsorbents is rabotnom us technical solution to the problem of decontamination and selection of catalysts di - and oligomerization of ethylene is the way, where as decontamination systems use water-base or water-ammonia solutions (application Japan N 3-220135 from 24.01.1990; R j Chem. 1993, AP). These solutions are used for the separation of the deactivated catalyst from oligomerizate. This followed a water-base or water-ammonia allocation spent the deactivated catalyst oligomerizes subjected to additional washing with demineralised water.

Lye and ammonia include decontamination system in the first place to ensure the neutralization of the hydrogen chloride formed by the hydrolysis of chlorine-containing reaction products KMK di - or oligomerization of ethylene.

This method also has significant drawbacks.

The use of this method of decontamination and selection KMC di - or oligomerization of ethylene in water-base or water-ammonia washing oligomerizate leads to the formation of a large number of chemically contaminated water runoff.

On the other hand, slow and insufficient mixing of water and cleofas in devices with mixers or widely used diaphragm mixers leads to the formation of cationic active centers, Protheroe feature of all known methods, that deactivation of the catalyst and the selection of the deactivated catalyst is produced in two stages before the separation of oligomerizate on a narrow faction.

The aim of the present invention is to increase the purity of the LAO, i.e. increasing the selectivity of the catalyst and process of the di - or oligomerization of ethylene.

Another objective of the present invention is the simplification of technological design stages of deactivation of the catalyst is di - or oligomerization of ethylene and selection of the deactivated catalyst from the reaction mass.

Another objective of the present invention is the complete elimination of education in the process of chemically contaminated water drains and ensuring environmental cleanliness of the process.

These goals are achieved developed a method of decontamination KMC homogeneous processes, such as dimerization or oligomerization of ethylene in LAO, and its separation from the organic reaction mixture by mixing it with a solution of the hydroxide of the metal in protonotaries the solvent and the selection of the deactivated catalyst from the organic phase in a single stage at a temperature of 60 - 80oC and a pressure of ethylene of 2 to 4 MPa.

Decontamination "live" to the same conditions.

In accordance with the invention, the process of deactivation of the catalyst solution of hydroxide of the metal in protonotaries solvent flexible in terms of the temperature - it has almost no influence on the rate of deactivation and selectivity to the LAO. However, to ensure a high selectivity of the process by LAO deactivation of the catalyst should be carried out at elevated pressures of ethylene.

The selected pressure range provides a high rate of deactivation of KMC and high selectivity of the process.

The rate of deactivation of the catalyst and the selectivity to the LAO significantly dependent on the efficiency of mixing the above-mentioned solutions. Therefore, the mechanical mixing of the organic phase with a solution of the hydroxide of the metal in protonotaries solvent additionally intensify the irradiation of a mixture received by the ultrasound.

As a device for ultrasonic treatment of mixed liquids using a three-dimensional lattice with magnetostriction, which is placed in the mixer oleo - and aqueous phase and is associated with a generator of ultrasonic radiation, the office of the Ombudsman is 2.5. Ultrasonic irradiation increases the degree of disperse Ultrazvuk in chemical engineering. Kiev, Ukrniinti, 1970; Collection "Thermoelectricity disperse systems", Kiev, Naukova Dumka, 1971). Achieved while improving the quality of mixing of oligomerizate with an aqueous-alkaline solution and increase the stability of the obtained dispersion contribute to the increase in the rate of deactivation of the catalyst and increase the selectivity of the process.

After deactivation of the catalyst protonotaries solvent is recovered from the reaction mass by distillation and adsorption purification, and the deactivated catalyst remains in the organic phase. Selected protonotaries solvent return in recycling for the preparation of alkali solution. This eliminates the formation of chemically contaminated wastewater and provides ecological purity of the process.

As protonotaries solvent to prepare solutions of the metal hydroxide used for the deactivation of the catalyst, use water, alcohol or ammonia. The concentration of the hydroxide of the metal in protonotaries solvent ranges from 1 to 40 wt.%.

Preferred are solutions containing from 5 to 10 wt.% the hydroxide of the metal.

As a hydroxide of the metal hydroxide use, SEL is beryllium, magnesium hydroxide, calcium hydroxide and aluminum hydroxide. The last of poorly soluble compounds and their use in suspension.

Despite significant efforts to study reactions between the components of KMC in the process of di - or oligomerization of ethylene and model conditions, the exact composition of the products of these reactions are unknown. This eliminates the possibility of a reasonable and accurate description of the chemistry of processes decontamination live catalysts di - or oligomerization of ethylene in water-, alcohol - or ammonia solutions of metal hydroxides. The available data suggest that only about a probable chemical composition of these processes.

It is generally accepted that the active center of the oligomerization of ethylene includes circinelloides compound containing Sigma zirconium-carbon bond, for example, it is Obvious that in the process of water-, alcohol - or ammonia-alkaline decontamination live KMC will happen hydrolysis or alcoholysis of these relations

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Because the active centers in KMC very little, the main mass decontamination agent will be consumed in reactions with the components of KMC.

As an example, consider the assumed chemical composition of the water-alkaline decontamination To>(Al/Zr = 13). Based on the results of a study of the hydrolysis of a single component of this system is an aqueous-alkaline solutions in toluene, the chemistry taking place in desactivate reactions very roughly can be reflected by the following scheme:

Zr(Osoite3H7)4+ 4NaOH ---> Zr(OH)4+ 4NaOCOC3H7;

13(C2H5)1,5AlCl1,5+ 19,5 H2O ---> 19,5 C2H6+ 13(HO)1,5AlCl1,5;

13(HO)1,5AlCl1,5+ 19,5 NaOH ---> 13Al(OH)3+ 19,5 NaCl;

13Al(OH)3+ 13NaOH ---> 13NaAlO2+ 26H2O.

Summing the left and right part of the above four equations, and performing simple arithmetic reduction, get balanced gross equation

Zr(Osoite3H7)4+ 13(C2H5)1,5AlCl1,5+ 36,5 NaOH ---> Zr(OH)4+ 4NaOCOC3H7+ 19,5 C2H6+ 19,5 NaCl + 13NaAlO2+ 6,5 H2O.

This equation reflects the features and stoichiometry flowing in desactivate reactions. It is seen that the main decontamination agent in this system is sodium hydroxide. To ensure complete decontamination is advisable to use 10 to 20% excess of sodium hydroxide with respect to the stoichiometry of these reactions.

After separation of proton-donor action of the solvent in refuse in the form of a finely dispersed suspension contains insoluble in hydrocarbons unspent sodium hydroxide, sodium chloride, aluminates and zirconate sodium, hydroxychloride aluminum and zirconium hydroxides and oxides of aluminum and zirconium, as well as itmelancholy sodium. From alafasy are removed by the method of the inertial-gravitational sedimentation or filtration separation or after separation alafasy on individual components and narrow cut by means of atmospheric-vacuum evaporating device in the system of columns at temperatures of 60 to 300oC.

The use of the second variant of the developed method was made possible thanks to the fact that as a result of targeted research using model and real object, it was found that LAO themselves and in the presence of the products of water-, alcohol - or ammonia-alkaline decontamination KMC di - or oligomerization of ethylene at temperatures 60-300oC thermally stable and do not undergo any transformations.

As the selection of individual components and narrow fractions of EA gradually increases (10-20 times). After separation alafasy on individual components and narrow faction of the deactivated catalyst together with traces formed of polyethylene and waxy LAO falls into the VAT residue.

Separation of the products of decontamination of spent catalyst and waxy LAO in accordance with the invention produce extraction method.

The essence of this solution is that waxy olefins contained in the VAT residue, extracted with a hydrocarbon, mainly boiling solvent selected from the group comprising isopentane, hexane, heptane, gasoline, benzene, toluene, butene-1, hexene-1 and octene-1, and the aforementioned products deactivation of the catalyst in the form of sludge after washing the used solvent is sent in the form of a suspension in a settling tank, a filter or a centrifuge, where they are separated from the hydrocarbon solvent.

Economic reasons as the extractant, it is recommended to apply the solvent, which is used or formed during the oligomerization. By extracting the ability of the best among these extractants for waxy LAO is toluene.

The separation of ikitelli mineralization) in the spray fire (flaming) dryer, and from it comes to recycling, i.e. the recovery of sodium, aluminum and zirconium. Recovery of zirconium, in particular, metallurgical method is advantageous in the case when the content of zirconium in the dry sludge exceeds 3 wt.%. This case occurs when decontamination and separation of waste zirconium-aluminium-containing KMC oligomerization of ethylene.

Waxy LAO from the extract combined with the wash hydrocarbon solution, isolated by distillation of the hydrocarbon solvent. The selected hydrocarbon solvent in return for recycling extraction waxy LAO from VAT residue, and waxy LAO sent for recycling or to the warehouse.

Block diagram stage decontamination live KMC di - or oligomerization of ethylene and selection of products formed deactivation of the catalyst from oligomerizate shown in Fig.1. It includes the following nodes:

1 - site preparation of a solution of metal hydroxide;

2, 3 - site decontamination KMC di - or oligomerization of ethylene, equipped with a device and a generator (3) ultrasonic irradiation mix of alafasy with a solution of a metal hydroxide in protonotaries solvent;

4 - node allocation protectii LAO;

6 - node extraction separation of waxy LAO products and the decontamination of KMC di - or oligomerization of ethylene;

7 - settling centrifuge or Druk-filter;

8 - node separation of treated waxy LAO;

9 - node high-temperature oxidative mineralization highlighted the deactivated catalyst (spray dryer fire);

10 - cyclone-dust-catcher.

The second alternative technologies decontamination and selection of the deactivated catalyst from alafasy includes the following nodes (Fig.2):

1 - site preparation of a solution of metal hydroxide;

2, 3 - site decontamination KMC di - or oligomerization of ethylene in water, alcohol or ammonia (protonotaria) a solution of a metal hydroxide, equipped with a device and a generator (3) irradiating the mixture with ultrasound;

4 - node allocation protonotaries solvent;

5 - site selection of the deactivated catalyst and high molecular weight polyethylene (sludge centrifuge or Druk-filter);

6 - node high-temperature oxidative mineralization highlighted the deactivated catalyst (spray dryer fire);

7 - cyclone-dust collector;

8 - uz is aktivacii and selection of the deactivated catalyst includes the following nodes (Fig.3):

1 - site preparation of a solution of alkali;

2, 3 - site water-alkaline deactivation of the catalyst is di - or oligomerization of ethylene, where 2 - mixer-deactivator; 3 - washer-sump;

4, 5 - site water rinse oligomerizate, where 4 - faucet-washer; 5 - washer-sump;

6 - node azeotropic drying of oligomerizate;

7 - site atmospheric vacuum separation oligomerizate on individual components and narrow faction;

8 - site carbon dioxide neutralization water drains;

9 - settling or filtration centrifuge;

10, 11 - site recycling of the catalyst slurry, where 10 is the spray dryer fire; 11 - multicyclone;

12 - node separation of hydrocarbons dissolved in the wastewater.

The diagrams show the direction of the main raw materials and material flows.

The mapping shown in Fig. 1 - 3 flowchart stage decontamination and allocation of spent catalyst, di - and oligomerization of ethylene in the LAO suggests that the patented method has a simpler technological design and is characterized by complete absence of sewage. An important distinguishing feature of the patented method is that this is the lia, and what demineralized water for washing oligomerizate and gaseous carbon dioxide to neutralize the water drains in the patented method is generally not used.

In the newly developed method can be used in homopathic processes di-and oligomerization, metathesis, telomerization, hydrogenation, alkylation of other monomers with soluble titanium-, zirconium-, hafnium-, Nickel-, molybdenum-, tungsten - and other transition metal-containing KMC.

The invention is confirmed and illustrated by (but not limited to) the following examples.

Example 1.

1.1. The oligomerization of ethylene was carried out on the system Zr(Osoite3H7)4(0,382 mmol) (0,0348 g of zirconium) + (C2H5)1,5AlCl1,5(Al/Zr=13) in toluene (0.25 l) at 80oC and a pressure of ethylene of 2.0 MPa for 60 minutes. As a result of oligomerization was trashdolls to 187.5 g of ethylene were formed 250 ml LAO.

1.2. Deactivation of the catalyst in oligomerizate ( 500 ml) was performed in an aqueous-alkaline solution containing 15 ml of water and 3.4 g of sodium hydroxide (to 18.5 wt. %), directly in the reactor in the above-mentioned conditions under intensive stirring of oligomerizate and decontamination solution for the and for the irradiation of miscible liquids by ultrasound. 20 minutes after loading into the reactor an aqueous alkali solution, a sample was taken of oligomerizate for various tests, the temperature of the reaction mass was reduced to 20-25oC and produced throttling ethylene. In the throttling process together with ethylene from the reactor withdrew almost all the resulting butene-1. Following this, the reaction mass was discharged from the reactor. After unloading from the reactor separation of the reaction mass at oleo - and aqueous phase and the separation from it of precipitation was not observed.

1.3. The resulting reaction mass ( 500 ml) containing products deactivation of the catalyst were loaded into a cube highly efficient speakers for atmospheric and vacuum pickup of oligomerizate.

First, at temperatures of 60-70oC was carried out azeotropic dehydration of oligomerizate. From Florentine were selected to 14.2 ml of water. This is a 94.6 wt.% per loaded in the reactor water.

1.4. After drying produced the selection from oligomerizate hexene-1, toluene, octene-1, mission-1 and fractions LAO C12- C18. After the pickup of oligomerizate at a fraction of the cube speakers in a hot state was uploaded 30 g milk-white homogeneous VAT residue. Highlighted in blue is"ptx2">

1.5. Received VAT residue (30 g) was loaded into a glass reactor with a jacket for temperature control, equipped with a helical stirrer with an Electromechanical drive. There also downloaded 280 ml of toluene. The result is stirring the obtained mixture at 80oC for 20 minutes formed a solution of waxy LAO and suspension products deactivation of the catalyst. The precipitate from the solution waxy LAO in toluene after settling was separated by decantation. Then to the precipitate was added to 100 ml of fresh toluene. The resulting suspension was stirred for 20 minutes in the above-described conditions. The residue from the leaching solution separated in the centrifuge, the resulting centrate combined with the previously separated solution LAO in toluene.

1.6. Selected products deactivation of the catalyst was dried in an oven at 300oC in air atmosphere for 60 minutes. Received 3,82 g of sediment. For analysis on Zr took 0,0111 g of sediment and dissolved it in 3 ml of a standard analytical solution. A colorimetric method was found that 0,0111 g of sediment contain 9510-6zirconium. From this it follows that 3,82 g of sediment contain 0,0327 g of zirconium (94 wt.% in the calculation of the original zirconium (0,0348 g), loaded into the reactor in the form Zr (Ososo C3H7Asia and stick to the surface of the reactor, flasks and pipettes.

As a result of tests on aluminum and chlorine found that the selected sediment contains of 0.13 g of aluminum (97,2 wt.% in the calculation of the original aluminum (0,1342 g), introduced in the reactor in the form (C2H5)1,5AlCl1,5and 0,253 g chlorine (95.6 wt.% in the calculation of the original chlorine (0,266 g), loaded into the reactor in the form (C2H5)1AlCl1,5).

1.7. The combined solution waxy LAO in toluene (370 ml) was loaded into the cube atmospheric-vacuum distillation column and at 111oC and atmospheric pressure drove the bulk of the toluene. The remains of toluene from waxy olefins were removed in vacuum with the use of traps cooled by liquid nitrogen. Just clubbed 361 ml (95%) of toluene. From the cube unloaded 24,1 g waxy LAO (12,85 wt.% in the calculation used in the oligomerization of ethylene).

1.8. In table. 2 shows the group structure LAO isolated from oligomerizate received the deactivation of the catalyst under conditions of ultrasonic irradiation miscible liquids and in the control conditions without ultrasonic irradiation. The comparison of the obtained data shows that ultrasonic irradiation mix of oligomerizate and water solution is content in the fractions LAO olefins with vinyl and vinylidene double bonds and the complete elimination of the alkylation.

Example 2.

2.1. Dimerization of ethylene is conducted in the system Ti(OHC4H9)4-Al(C2H5)3in the environment of diethyl ether. In a reactor with a volume of 1.1 l loaded with 0.2 l of diethyl ether, 0,1875 g (0.55 mmol) of tetrabutoxide titanium and 3.11 g (27,28 mmol) of triethylaluminum (Al/Ti=49,6). When 40oC and a pressure of ethylene of 8.0 at 250 minutes trashdolls 435 g (7,768 mol) of ethylene. The average rate of dimerization of 8.5 g C2H4/(Lmin) (0,52 kg C4H8/(LCH)). The yield of butene-1 = 2,32 kg/t Ti(OHC4H9)4or 14100 mol of butene-1 per 1 mol Ti(OHC4H9)4. CIS - and TRANS butenes-2, and polyethylene products were absent. Along with butene-1 was formed of 9.1 g of hexene and octenol (2.1 wt.% based on the butene-1).

2.2. Deactivation of the catalyst in the reaction mass (900 ml) was performed in an aqueous-alkaline solution containing 15 ml of water and 0.15 g (3.75 mmol) of sodium hydroxide (0.99 wt.% in the calculation of the water) directly into the reactor in the above-mentioned conditions with vigorous stirring of the reaction mass of the solution for 20 minutes using a shielded electromagnetic stirrers and built in the bottom of the reactor device for irradiating the resulting mixture with ultrasound. After 20 minutse.

2.3. The resulting reaction mass containing diethyl ether, butene-1, hexene and octene, water and decomposition products of the catalyst present in the reactor pressure ethylene predavlivali in metal cube reaction column equipped with a reflux condenser and Florentine vessel. Beginning at 20-30oC was made throttling of ethylene, and then at 0-5oC - azeotropic dehydration reaction mass. From Florentine were selected 11,0 ml of water, which is 73,3 wt.% per loaded in the reactor water.

2.4. After drying produced a selection of butene-1, diethyl ether and hexene. After acceleration in the cube speakers remained VAT residue containing octene, a small amount of a resinous unidentified substances and products deactivation of the catalyst (presumably hydroxides of titanium, aluminum and sodium, and sodium aluminate).

2.5. In the cube column was loaded with 100 ml of n-heptane. In the result of mixing the mixture at 20oC for 20 minutes using the flexible stirrer, which was introduced into the cube through the side nozzle, formed a solution of a resinous products and suspension products deactivation of the catalyst. The precipitate and the solution was unloaded in ryvnogo solution was separated in a centrifuge, the resulting centrate combined with the previously separated n-heptane solution.

2.6. Selected products deactivation of the catalyst was dried and progulivali in a muffle furnace at 600oC in air atmosphere for 60 minutes. Received 1,53 g sediment containing 0,0246 g titanium (92,8% by weight per loaded into the reactor titanium as Ti(OHC4H9)4), and 0.70 g of aluminum (95,1 wt.% per loaded into the reactor aluminium as Al(C2H5)3).

2.7. The combined n-heptane solution (130 ml) was loaded into the cube atmospheric-vacuum distillation column and at 98oC and atmospheric pressure drove the mass of n-septate. Remaining n-heptane was removed under vacuum using a trap cooled by liquid nitrogen. Just clubbed 128 ml (91,4%) n-heptane. From the cube in the hot condition unloaded 1.1 g of oily substance (0.25 wt.% in the calculation of the consumed ethylene).

Examples 3-14.

Loading the reagents into the reactor and the conditions of the oligomerization of ethylene in LAO were the same as in example 1. Deactivation of the catalyst in oligomerizate held water, alcohol and ammonia solutions of alkali directly in the reactor with mechanical stirring mix of rest the ptx2">

In examples 3-14 varied nature of the solvent for the alkali, the nature and concentration of alkali (PL. 3). All subsequent separation of the reaction mixture into fractions, separation and processing of products deactivation of the catalyst Zr(Osoite3H7)4- (C2H5)1,5AlCl1,5were the same as in example 1. Complete selection of zirconium, aluminum, and chlorine in the calculation of the original loading of these elements as components of the catalyst are given in table. 3. Despite the increased consumption of water, hydroxides of magnesium, calcium and beryllium dissolved only partially, and the aluminum hydroxide is practically not dissolved. They were introduced into the reactor in the form of a suspension.

The data obtained indicate that the preferred are aqueous solutions of sodium hydroxide.

Together, these results suggest that the patented method allows you to deactivate the catalyst, to increase the selectivity of the process and almost quantitatively to allocate deactivated KMC from oligomerizate, to eliminate formation of chemically contaminated waste water, to simplify the technological design and to ensure environmental cleanliness of the process.

Sources informalisation, 1447811.

5. Patent Of Great Britain, 1447812.

6. Patent Germany, 2274583

7. Patent Germany, 2462771.

8. USSR author's certificate, 1042701, 19.06.78.

9. Application Italy, 24498.79.

10. Patent Germany, 4338414, C 08 F 110/02, 1993.

11. Patent Germany, 4338416, C 08 F 4/642, 1993.

12. U.S. patent, 4486615.

13. Patent Germany, 4338415, C 08 F 6/03, 1993.

14. Japan's Bid 3-220135, 1990.

1. The method of decontamination of a complex ORGANOMETALLIC catalyst homogeneous processes, such as dimerization or oligomerization of ethylene to linear alpha-olefins, and its separation from the organic reaction mixture by mixing it with a solution of the hydroxide of the metal in protonotaries solvent, characterized in that the deactivation and the allocation of the catalyst from the organic phase is carried out in one stage.

2. The method according to p. 1, wherein mixing the organic phase with a solution of the hydroxide of the metal in protonotaries solvent additionally intensify the irradiation of a mixture received by the ultrasound.

3. The method according to p. 1 or 2, characterized in that protonotaries the solvent is released from the reaction mass by distillation, and the deactivated catalyst remains organic phase separated from the cubic remainder of the last separation column, containing the deactivated catalyst and waxy linear alpha olefins (LAO), after reaction mass is separated into fractions.

5. The method according to PP.1 to 4, characterized in that the selection of the deactivated catalyst from VAT residue includes extraction waxy LAO hydrocarbon solvent, inertial-gravitational settling of the deactivated catalyst from the hydrocarbon extract and subsequent high temperature oxidation mineralization highlighted the deactivated catalyst.

6. The method according to PP.1 to 5, characterized in that the hydrocarbon solvent for the extraction of waxy LAO from VAT residue recent separation column containing deactivated catalyst and waxy linear alpha-olefins, after reaction mass was separated into fractions using a hydrocarbon solvent selected from the group comprising isopentane, hexane, heptane, gasoline, benzene, toluene, butene-1, hexene-1, octene-1.

7. The method according to PP.1 - 6, characterized in that the deactivation of the catalyst used solutions containing 1 to 40 wt.% the hydroxide of the metal.

8. The method according to PP.1 - 7 of law, selected from the group comprising hydroxides of lithium, sodium, potassium, beryllium, magnesium, calcium, aluminum and ammonium.

9. The method according to PP.1 to 8, characterized in that the deactivation of the catalyst is carried out at 60 - 80oC and 2 to 4 MPa.

10. The method according to PP. 1 to 9, characterized in that the waxy linear alpha-olefins from an extract that contains a hydrocarbon solvent and waxy linear alpha-olefins, isolated by distillation of the hydrocarbon solvent.

11. The method according to PP.1 to 10, characterized in that the deactivated catalyst is separated from the organic phase to the separation of linear alpha-olefins into fractions.

 

Same patents:

The invention relates to a method of removing catalyst residues from polyisobutylene obtained in the presence of halides of titanium and trialkylamine in hydrocarbon solvents, and the polymer is used as the additive (directly or after modification) to motor and diesel oils for the manufacture of glue and other purposes

The invention relates to petrochemical technology, in particular to methods for selection of aromatic hydrocarbons from mixtures thereof with non-aromatic liquid extraction, and can be used in oil and chemical industry

The invention relates to the refining and petrochemical industry, in particular to a technology for obtaining new petrochemical products, and can be used in oil refining, petrochemical and gas industry

The invention relates to the refining and petrochemical industries, in particular solvents for the separation of hydrocarbon fractions by chemical composition

The invention relates to mass transfer processes in chemical technology, in particular, to methods of extraction desulfation hydrocarbons (NSO) of the alcohol solution of the secondary alkyl sulphates and sodium (ASN), and can be used in the production of surface-active substances used as the basis of synthetic detergents, foaming agents, and other chemical products

FIELD: petroleum processing, petroleum chemistry.

SUBSTANCE: method involves extractive rectification of gasoline fraction and the following extraction of distillate with mixed solvent N-methylpyrrolidone - sulfolane. At stage of extractive rectification mixed solvent N-methylpyrrolidone - sulfolane containing 60-80 wt.-% of N-methylpyrrolidone is used, and at stage of extraction the same mixed solvent N-methylpyrrolidone - sulfolane containing 80-95 wt.-% of sulfolane is used. Method provides simultaneous isolation of highly purified aromatic (C6-C8)-aromatic hydrocarbons from gasoline fractions with the extraction degree 99.8%.

EFFECT: improved method for isolating.

2 tbl, 1 ex

FIELD: chemistry.

SUBSTANCE: invention includes the primary methanol separation on the hydrophilic ultrafine or superfine fiber up to the residual methanol concentration no more than 250 mg/l of the liquid hydrocarbons, extraction of the methanol from liquid hydrocarbons with water, separation of the water solution of methanol from liquid hydrocarbons, removal of the purified hydrocarbons and water solution of methanol, if necessary the removal of the residual water solution of methanol from liquid hydrocarbons with sorption and following desorption and/or catalytical conversion obtaining hydrocarbons and water.

EFFECT: decrease of the energy consumption and efficiency increase in the process of liquid hydrocarbons purification from water methanol solution.

2 cl, 7 ex, 9 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of extracting oxidised sulphur compounds, particularly sulphoxides and sulphones, from a mixture with hydrocarbons and sulphur compounds by treating the mixture with an extractant in weight ratio raw material: extractant from 1:1 to 1:7, and temperature from 30 to 70C. The extractant used is isopropyl alcohol with water content from 30 to 50 vol. % (36.55-59.77 wt %) and hydrocarbon content from 0.05 to 0.1 wt %.

EFFECT: high content of sulphoxides and sulphones in the concentrate.

7 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: present invention relates to an ethylene oligomerisation method. The method involves the following steps: (i) oligomerisation of ethylene in a reactor in the presence of a solvent and a catalyst composition; (ii) outlet of a product stream containing the catalyst composition from the reactor; (iii) deactivation and extraction of the catalyst composition with a polar phase, wherein the product stream and the polar phase are mixed in a dynamic mixer having a rotor and a stator, having concentric operating rings which are cut and/or bored radially, wherein the annular gap lies in the range from 0.1 to 5 mm. The invention also relates to a reactor system for realising said method.

EFFECT: present invention enables to easily and quickly deactivate and extract a catalyst composition from an organic product stream of an oligomerisation reactor.

8 cl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing isoprene via liquid-phase reaction of formaldehyde and isobutylene and/or substances which are sources thereof, for example, 4,4-dimethyl-1,3-dioxane and trimethyl carbinol, in the presence of an aqueous solution of an acid catalyst at high temperature and pressure while extracting a vapour-liquid stream of reaction products and water from the reaction zone. Further, the vapour-liquid stream is separated, cooled, condensed and split into aqueous and oily layers, followed by extraction of isoprene from the oily layer. The method is characterised by that before extracting isoprene, the oily layer is washed with water in a countercurrent column at temperature 20-60C, pressure 0.4-1.0 MPa in weight ratio (10-50):1, respectively.

EFFECT: method reduces loss of isoprene during extraction thereof.

3 cl, 1 tbl, 4 ex, 1 dwg

FIELD: power engineering.

SUBSTANCE: method to produce liquefied hydrocarbon gases includes stabilisation of a deethanised gas condensate by extraction of hydrocarbon gases from it, their cooling, mixing of liquefied hydrocarbon gases (LHG) with water, washing of methanol and phase separation into LHG and a water-methanol solution. At the same time at the washing stage the mixture of LHG with water is dispersed in water phase, then coalescence of finely dispersed drops of the water-methanol solution is carried out, afterwards phase separation is carried out. A plant to produce liquefied hydrocarbon gases comprises the following serially joined components: a rectification tower of gas condensate stabilisation, a cooling device, a mixing device, at least one reservoir for methanol washing and a separating reservoir. At the same time at least one reservoir for methanol washing and the separating reservoir are arranged in the form of sections of a reservoir filter, separated by two partitions with coalescent filter cartridges installed in them to form three sections in the inner cavity of the specified filter, besides, two sections represent reservoirs of methanol washing, and the third section - a separating reservoir.

EFFECT: using the invention will make it possible to minimise capital and current costs for a plant due to its simplification.

5 cl, 3 dwg

FIELD: oil and gas industry.

SUBSTANCE: selective dissolvent is a mixture containing 15-30 wt % of N-methyl pyrrolidone, 65-80% triethylene glycol, 3-7 wt % of water.

EFFECT: using this invention makes it possible to increase extent of extraction of aromatic hydrocarbons from reforming catalysate.

1 cl, 4 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to two versions of the method of using dimethyl ether (DME) synthesis products to convert oxygenates to olefins. One of the versions comprises the following steps: extracting from a DME reactor a stream containing DME, water and methanol; separating, in a liquid-gas separator, carbon dioxide gas from the stream from the DME reactor to obtain a degassed output stream; feeding the degassed output stream into a DME column to obtain crude DME material and a solvent stream containing methanol and water; feeding the crude DME material into a reactor for converting oxygenates to olefins to obtain an olefin-containing output stream which also contains oxygenates; separating the olefin-containing output stream to obtain a fraction containing light olefins and a fraction containing heavy olefins, wherein the fraction containing light olefins contains ethylene and the fraction containing heavy olefins contains C4+; bringing the fraction containing light olefins into contact with a first portion of a solvent stream in a first zone of reacting with solvent to obtain a first olefin-containing purified stream and a first oxygenate-containing extract; bringing the fraction containing heavy olefins into contact with a second portion of the solvent stream in a second zone for reacting with solvent to obtain a second olefin-containing purified stream and a second oxygenate-containing extract.

EFFECT: disclosed method enables integration of dimethyl ether synthesis with conversion of oxygenates to olefins.

8 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to method of reducing acidity of hydrocarbon raw material, which includes: (a) contact of hydrocarbon raw material, which contains organic acid, with phosphonium ionic liquid, non-mixable with hydrocarbon raw material, including tetrabutyl phosphonium methane sulfonate, with obtaining mixture, which contains hydrocarbon and said liquid; (b) separation of mixture with obtaining effluent, which contains hydrocarbon, and effluent, which contains phosphonium ionic liquid, containing organic acid. In addition, method includes contact of effluent, which contains ionic liquid, with regenerating solvent and separation of effluent, containing ionic liquid, from regenerating solvent with obtaining flow of extract, which contains organic acid, and flow of regenerated ionic liquid, which contains phosphonium ionic liquid, non-mixable with raw material, where regenerating solvent contains water, and flow of regenerated ionic liquid additionally contains water and where effluent, which contains hydrocarbon, contains phosphonium ionic liquid, non-mixable with raw material, additionally including washing of, at least, part of effluent, which contains hydrocarbon, with water with obtaining effluent, containing washed hydrocarbon, and flow of waste water, and flow of waste water contains phosphonium ionic liquid, non-mixable with raw material; with, at least, part of flow of waste water being, at least, part of regenerating solvent.

EFFECT: claimed method can ensure removal of up to eighty percent of organic acids from hydrocarbon.

10 cl, 2 dwg, 5 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: method of inhibiting polymerisation of vinyl aromatic compounds during extractive distillation includes the following steps: a) providing a mixture containing styrene; b) adding one 2-sec-butyl-4,6-dinitrophenol (DNBP) inhibitor to the mixture; and c) performing extractive distillation of the mixture after step b) to of separate styrene; d) forming less than 200 ppmw of a polymer from the styrene.

EFFECT: minimum polymer formation.

5 cl, 1 tbl, 1 ex

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: method comprises: (i) treating polymeric glue containing unsaturated polymer, in inert water-immiscible liquid, with hydrogen source in presence of hydrogenation catalyst; (ii) contacting polymeric glue from stage (i) with one or several aqueous solutions of a weak acid having pKa 1.5 and higher (25ºC); (ii) contacting polymeric glue from stage (ii) with one or several aqueous solutions of a weak base having pKa 10.5 or lower; and (iv) recovering hydrogenated polymer.

EFFECT: enabled preparation of essentially colorless hydrogenated polymers.

11 cl, 1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method for producing polymeric petroleum resins. The invention describes a method of producing polymeric petroleum resins which involves polymerisation of unsaturated compounds of the fraction of liquid products of pyrolysis of straight-run petrol with boiling range of 130-190C in the presence of catalyst systems: titanium tetrachloride and an organoaluminium compound in molar ratio: TiCL4 : Al(C2H5)2Cl = 1:(0.1-3.0); TiCl4 : Al(C2H5)3 = 1:(0.1-3.0); TiCl4 : Al(iso-C4H9)3 = 1:(0.1-3.0).The method is distinguished by that the catalyst is deactivated with triglycidyl ethers of polyoxypropylenetriols manufactured under the trademark Laproxide 603 and Laproxide 703, having general formula:

, where a, b, c = 1-3, with molecular weight of 434-782, and taken in molar ratio to the catalyst system of 1.0:2.1.The deactivation products remain in the composition of the polymeric petroleum resins.

EFFECT: simple technology of producing polymeric petroleum resins, improved environmental safety of the process, improved sanitary and hygienic conditions during production.

1 cl, 3 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to a method of extracting transition metals from polymer solutions. Described is a method of extracting transition metals from polymer solutions after atom transfer radical polymerisation (ATRP), characterised by that the transition metal compounds are precipitated by adding mercaptan or compounds having a thiol group as a precipitant and then removed by filtering.

EFFECT: efficient removal of transition metal complexes from polymer solutions.

18 cl, 1 tbl, 3 ex

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