Method of preparing chromium oxide catalyst on inorganic carrier as component of double ethylene copolymerization catalytic system

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to chromium oxide catalysts on inorganic carriers as components of double catalytic systems also including supported chromocene catalyst and used for synthesis of high-strength, crack-resisting low-pressure polyethylene. According to invention, preparation procedure comprises preliminarily drying silica (carrier), applying chromium and aluminum compounds thereon from solutions in organic solvent, removing solvent, drying resulting product and subsequent thermal-oxidative activation in dry air flow within temperature range between 450 and 750°C. Long-term polymerization activity of double catalytic system is achieved owing to using, as aluminum compound solution, solution of alkoxyalumoxane of general formula [Al(OR)n (OR')1-nO]m, where R denotes ethyl or isopropyl, R' group C6H9O2, n = 0.6 or 0.7, and m = 2-5, in water-free lower aliphatic alcohol and. as chromium compound solution, solution of dicyclopentadienylchromium in toluene, and preliminary drying of silica is carried out in fluidized bed in presence of ammonium hexafluorosilicate at constant temperature within the range 330-400°C. Invention is also characterized by that thermal-oxidative activation of catalytic product is followed by thermal-reductive activation thereof in flow of purified nitrogen mixed with dry carbon dioxide at constant temperature within the range 350-390°C.

EFFECT: prolonged long-term catalytic activity.

3 tbl, 22 ex

 

The present invention relates to methods for the polymerization catalysts containing chromium oxide, mounted on a solid inorganic oxide carrier of nature, i.e. ocenography catalysts (UCC), which is one of the components of the dual catalytic systems (CS), also containing chromitovy catalyst (CCK) on inorganic carrier and used for the synthesis of high-density polyethylene (HDPE) in the copolymerization of ethylene with a relatively small number of α -olefin (propylene, butene-1, hexene-1 and other) in suspension, solution or gas phase processes.

It is known [U.S. patent No. 5624877, MKI608 F 004/24, publ. 1997; U.S. patent No. 5648439, MKI608 F 4/24, publ. 1997], the double CC (UCC-CCK) provide in a single polymerization reactor HDPE containing high molecular weight branched copolymer (low density) fraction formed at UCC, and non-branched low molecular weight (high density) fraction of input applied CCK.

This HDPE, having a density of not lower than 0.95 g/cm3, characterized by high values of some physical and mechanical properties, in particular resistance to cracking under stress, which is determined by the presence of high molecular weight branched copolymer fraction, and str is Chennai the processability, that ensures the presence of low molecular weight fractions. This combination of properties is particularly important for HDPE, reaching for the manufacture of high-strength pipes for transportation of gas and production of packaging films [Scheirs J., Bohm L.L., Boot J.C., P.S. Leevers, Trends in Polymer Science, 1996, v.4, N12, p.408-415; Schut J.H., Plast World, 1996, v. 54 N 9, p.43-44, 46, 48].

Known [U.S. patent No. 5624877, MKI608 F 004/24, publ. 1997] the method of obtaining oxenkrug catalyst is chromium oxide deposited on an inorganic oxide, which is a component of the double KS, including chromitovy catalyst on an inorganic carrier. This COP (UCC-CCK) is used in suspension, solution or gas phase polymerization of ethylene or copolymerization with α -olefins (such as 1-hexene). Considering they are applied on the carrier is silicon dioxide SiO2the silicate SiO2·Al2O3aluminium oxide Al2About3, fluorinated alumina Al2About3,F, silicon dioxide in combination with titanium dioxide SiO2·TiO2and so on, preferably SiO2or SiO2·TiO2, compounds of chromium, such as chromium nitrate from his alcohol solution or dicyclopentadienyliron of its hydrocarbon solution, followed by oxidative activation of the obtained product in the oxygen-containing gas, for example the er dry air, at a constant temperature in the range of 400-900° With (which resulted from the applied compounds of chromium trioxide is formed of chromium) and then reductive activation with the use of carbon monoxide in the temperature range of 300-500° (where CR6+as part of the UCC is restored to IG2+). Prepared deposited catalyst has the General structure CrO/SiO2or CrO/SiO2·TiO2and contains from 0.05 to 5, preferably from 0.5 to 2.0 wt.% chromium (in the specific examples describe the invention to the U.S. patent No. 5624877 see UCC only on these two media - SiO2industrial brands 969-MSLF or 969ID and SiO2·TiO2industrial brands Magnapore or Sylopore).

Dual CS using the received UCC is formed directly in a polymerization reactor in the reactor initially loaded UCC, and then of CCK on the media alumophosphate (corresponds to the formula IG(C5H5)2/lO4). Applied CCK contains from 0.01 to 10, preferably from 0.1 to 2.0 wt.% SG. According to U.S. patent No. 5624877 in the synthesis of HDPE in a single reactor in addition to this dual chrome KS is also used organoboron or alyuminiiorganicheskikh socialization in an amount corresponding to a mass ratio of boron or aluminum to chromium in the dual chrome KS from 0.5:1 to 10:1, preferred the part from 2:1 to 5:1, respectively. The resulting HDPE is characterized by multi - or bimodal molecular mass distribution (MMD) and has a high resistance to cracking under stress (>1000 h) when the density values 0,948-0,953 g/cm3and the melt flow index (MFR) at 190° defined with loads of 2.16 and 21.6 kg (MFR2,16and VKT21,6), respectively, 0.1-0.2 g/10 min and 35-37 g/10 min (see table 4 example 4 description of U.S. patent No. 5624877). The specified properties of HDPE determined on the samples subjected after synthesis mixture in the melt on a laboratory mixer Bunbury.

The disadvantage of this method of obtaining the UCC is the low catalytic activity of the obtained catalyst, characterized by the output of the synthesized copolymer of ethylene and correspondingly low activity of the COP on the basis of such UCC and applied CCK. Thus, when the suspension copolymerization of ethylene with 1-hexene (30 ml 1.2 liters of isobutane) with a total pressure of 39 at a partial hydrogen pressure of 2.5 and at a temperature of 95° using CC, consisting of a obtained as described above, the UCC composition CrO/SiO2containing 1 wt.% chromium, and dealt with CCK content of 2 wt.%. Cr(C5H5)2when the mass ratio of Cr(C5H5)2to SGAs, equal to 0.92, in combination with socialization - triethylaluminium Al(C2H5) 3(1.7 mg/kg isobutane) receive 2650 g HDPE with 1 g KC for 1 h copolymerization, which corresponds to a yield 68 g of HDPE/g KC· h· at. In U.S. patent No. 5624877 is the activity of the COP process for copolymerization flowing quite short - 45-75 minutes However, the industrial implementation of gas-phase copolymerization of ethylene duration of the process is usually 4-8 h [Baulin A. A., Black A.I., Reznikov O.N., Standin A.M., Reservoir, mass, 1985, No. 3, p.6-8]. In the mentioned patent there is no information about saving activity of the COP in the given level for a long time (co)polymerization.

In addition, the disadvantages of the described method according to U.S. patent No. 5624877 are the necessity of using socializaton obtained on the basis of UCC CA - Al - or-organic compounds, and the use in the preparation of UCC media other chemical nature (SiO2or SiO2·TiO2) compared to medium (alumophosphates), primenyaemym in the preparation of CCK, which complicates the process of making the COP and, accordingly, the process of synthesis of the obtained copolymer of ethylene.

Also known [U.S. patent No. 6610799, IPC708 F 004/44; 08 F 004/62, publ. 2003] the method of obtaining the UCC on the media (silicon dioxide), a component of the catalytic system, including chromitovy catalyst on the e media - the silicon dioxide, suspension or gas-phase polymerization of ethylene or copolymerization with α -olefins. Such UCC they are applied on SiO2from the aqueous solution of chromium compounds (chromium trioxide or chromium triacetate), followed by oxidative activation in dry air at a temperature in the range of 500-950° (in the specific example of the description of U.S. patent No. 6610799 - at a temperature of 800° C for 16 h) and then his recovery activation in an atmosphere containing carbon monoxide, in the temperature range of 250-400° With recovery of CR6+in the composition of the catalyst before Cr2+(in the specific example of the description of the patent - in an atmosphere of a mixture of CO/N2containing 15% at a temperature of 380° C for 3.5 h). Double CC on the basis of the received UCC composition CrO/SiO2and CCK composition Cr(C5H5)2/SiO2formed by mixing powders of both catalysts before use in the process of (co)polymerization. When applying mixtures of catalysts in a polymerization reactor in suspension in a hydrocarbon solvent (pentane) to improve the fluidity of this COP in it add, for example, powdered zinc oxide ZnO.

Using the specified double chrome CC (UCC-CCK) receive multi - or bimodal HDPE suitable for the manufacture of fibers, films, pipes (concrete show is whether the density and resistance to cracking under stress HDPE in U.S. patent No. 6610799 not shown). The COP using UCC, obtained as described above, is more active than the COP according to U.S. patent No. 5624877, it does not require the use of Al or In-organic socializaton. Use as a carrier SiO2in the preparation of a UCC, and CCK simplifies the process of preparation of the COP.

However, UCC, obtained by the method according to U.S. patent No. 6610799 is not a high catalytic activity, characterized by the output of the synthesized HDPE, and correspondingly low level of the COP on the basis of such UCC and applied CCK. So the environment of isobutane process of suspension polymerization of ethylene with the total pressure (Ptotal) 38 at a partial pressure of hydrogen (HH2) 0.6 ATA and a temperature of 94° using the specified COP when the mass ratio of CrO/SiO2to Cr(C5H5)2/SiO21.0 (ratio of DSA/CR(C5H5)2excluding media in the patent is not specified), receive (total process time : 1 h) 3400-3500 g HDPE with 1 g KC per hour, which corresponds to the output 89-92 g HDPE/g KC· h· at (see the table of example 5, the description of U.S. patent No. 6610799). The activity of the COP during prolonged holding of the polymerization process (4-8 h) in the above patent is not given.

In addition, HDPE, synthesized under similar conditions, and eat unstable characteristics, for example, the TPP vary within the following limits: PTR2,16from 0.15 to 0.62 g/10 min, MFR21,6from 17 to 43 g/10 minutes

Closest to the claimed method of obtaining oxenkrug catalyst - component dual catalytic system suspension or gas-phase copolymerization of ethylene with α -olefins essential features - a method according to the patent of Russian Federation №2177954 [IPC708 F 4/02, 4/10, publ. 2002, prototype], according to which the UCC they are applied on pre-dried at 200° media - silicon dioxide in the form of silica gel from a solution in an organic solvent, namely the mixture of ethanol with acetone in a volume ratio of 1:(2-7), predecessors of chromium trioxide and oxides of aluminum and zinc in the composition of the prepared catalyst, which are used nonahydrate nitrate chromium (III) CR(NO3)3·9H2O, nonahydrate of aluminium nitrate Al(NO3)3·N2O and the uranyl nitrate zinc Zn(NO3)2·6H2O removal of solvent by evaporation, drying and subsequent oxidative activation product deposition in the stream of dry air at a given constant temperature in the range from 450 to 750° C for 2-5 hours, the Speed of temperature rise the temperature of the drying before it is acceptable constant value equal to 100-150° With/including Cooked applied catalyst composition SGAs3/SiO2·Al2O3·Zn contains from 0.4 to 4.0 wt.% chromium trioxide (0,21 to 2.1 wt.% IG), from 1.4 to 9.0 wt.% aluminum oxide, from 0.7 to 3.5 wt.% zinc oxide and from 83,5 to 97.5 wt.% (the rest) of silicon dioxide. Double KS, including collected in this way the UCC, is formed directly in the polymerization reactor by mixing it before copolymerization of ethylene with α -olefin both supported catalysts - UCC and CCK, and as CCK used industrial catalyst "S-9" by the company Union Carbide Corp. composition Cr(C5H5)2/SiO2obtained according to U.S. patent No. 3709853 [MCI 08 F 1/74, 3/06, publ. 1973].

Specified dual chrome KS used for the synthesis of copolymers of ethylene slurry and gas-phase methods. The advantage of the method of obtaining UCC according to the patent of Russian Federation №2177954 is the high activity of the UCC and, accordingly, the enclosing double KS (136-218 g HDPE/g KC· h· at), 2.0-2.4 times higher than the activity of the known COP in the above U.S. patents No. 5624877 and No. 6610799. Obtained according to the patent of Russian Federation №2177954 HDPE, characterized by a bimodal MMD, has good physical and mechanical properties: density 0,950-0,956 g/cm3, PTR2,16=0.04 to 0.34 g/10 min, MFR21,6=10,4-35,1 g/10 min, limit recuces and tensile 24,2-of 25.5 MPa, elongation at break 615-815%, resistance to cracking under stress more than 1000 hours (these figures are determined on samples of HDPE, homogenised after copolymerization synthesis by mixing in the melt on a laboratory roll mill).

The disadvantage of this method of obtaining UCC according to the patent of Russian Federation №2177954 is a low activity double COP with such a catalyst, for a long time copolymerization. So the maximum output PEND on the prototype at the time of gas-phase copolymerization of ethylene with butene-1, equal to 1 h was 218 g/g KC· h· at (see example 13 of the patent of the Russian Federation No. 2177954), while in the same polymerization conditions, but when the time 6 h, the average yield HDPE is 79 g/g KC· h· at (see the test case No. 22), i.e. there is a decline in the activity of CA in 2.8 times.

In addition, obtaining UCC using nitrates of chromium, aluminum and zinc, applied to the silicon dioxide, is associated with the release of nitrogen dioxide NO2at the stage of thermal-oxidative activation of the catalytic product. Nitrogen dioxide is a toxic substance, with the average daily maximum concentration in air of residential areas (MPCSS)equal to 0.04 mg/m3) [Besplatno G.P., moles Y.A., Maximum permissible concentrations of chemical substances in the environment. - L.: Chemistry, 1985, s.43].

The technical result, which provides the inventive method, is to increase long-term polymerization activity of the double CC on the basis of UCC obtained by the claimed method.

This technical result is achieved due to the fact that the method of obtaining oxenkrug catalyst on an inorganic carrier - dual component catalyst system for the copolymerization of ethylene, containing also applied chromitovy catalyst, including pre-drying of the carrier - silicon dioxide coating on the dried carrier compounds chromium and aluminum from their solutions in organic solvent, removing the solvent, drying the resulting product and its subsequent oxidative activation in a stream of dry air at constant temperature in the range from 450 to 750° as a solution of the aluminium compound used solution alkoxyalkane General formula

[Al(OR)n(OR')1-nO]m

where R=C2H5or ISO-C3H7;

R'=C6H9O2;

n=0.6 or 0.7;

m=2-5,

in absolute lower aliphatic alcohol as a solution of the compound of chromium - solution dicyclopentadienyliron in toluene, and the preliminary drying of the carrier - silicon dioxide is carried out in pseudowire the th layer in the presence of ammonium hexafluorosilicate at a constant temperature in the range of 330-400° With that, after thermal-oxidative activation of conduct termovosstanovleniyu activation of the catalytic product in the stream of the mixture purged with dry nitrogen monoxide at a constant temperature in the range from 350 to 390° C.

When conducting research in the field of synthesis of the UCC, which is a component of the COP, including CCK, the authors of the present invention, it was unexpectedly discovered that the method of preparation of UCC significantly affects long-term catalytic activity of the UCC and, respectively, on a long-term activity of the COP with that of the UCC. The combination of the above techniques: drying media (SiO2in the presence of ammonium hexafluorosilicate (where fluoridation of SiO2and use as precursors of oxides catalytically active metal SG and the modifier metal Al only organic derivatives of CR and Al - dicyclopentadienyliron SG(C5H5)2and alkoxyalkane (above specific composition) in the form of their solutions in organic solvents, followed by drying and oxidative and reductive activation of the obtained product known techniques, allows to obtain applied UCC composition CrO/SiO2F· Al2O3, who was part of the COP, including CCK (Cr(C5H5)2/SiO2 ), provides high activity of KS - 169-225 g HDPE/g KC· h· at that persists for an extended period of time, copolymerization of ethylene and at least 6 hours

In the known sources of information are data on the activity of the COP using the marked UCC only within 1 h (45-75 min) (co)polymerization of ethylene. As mentioned above, according to our data (see our reference sample No. 22) has the highest activity for 1 h copolymerization of ethylene COP using UCC and CCK according to the patent of Russian Federation №2177954 (218 g of HDPE/g KC· h· at) after 6 h copolymerization has catalytic activity of just 79 g HDPE/g KC· h· at, i.e. its activity 2.1-2.8 times lower than the activity of the COP using the UCC, obtained by the claimed method, in similar conditions copolymerization 6 hours.

To predict in advance the specified technical result it was impossible for the following reasons.

First, the fluoridation of media companies, operating in conjunction with applied CCK, can lead to an increase, but, on the contrary, a significant reduction in the activity of the double KS. As well known [U.S. patent No. 5543376, MKI608 F 4/24, publ. 1996]that the catalytic system based on UCC in fluorinated media - alumophosphate containing 1 wt.% F, with 2 wt.% SG as part of the UCC and adsorbirovannoi not what 0.26 wt.% SG(C 5H5)2provides during the suspension copolymerization of ethylene with hexene-1 when Rtotal=39 at PH2=2.5 at a temperature of copolymerization (tSOP) 95° output 1160 HDPE/g KC for 1 h copolymerization, and under all other equal conditions, but in the absence of fluorine in the composition of the medium UCC - 2380 g of HDPE/g CA (see example 4, table 4, experiments 404 and 405 of the said patent). Thus, the dual activity of the COP, including the UCC on the media without fluoride, is 61 g HDPE/g KC· h· ATA, and containing UCC in fluorinated media - a total of 30 g of HDPE/g KC· h· at., i.e. two times lower. Fluoridation media UCC in the method according to U.S. patent No. 5543376 perform processing media methanolic solution of hydrovhloride ammonium NH4HF2and subsequent thermal vacuum drying, i.e. a method that is different from the declare.

Secondly, the known higher activity double CC on the basis of the UCC and CCK for 1 h (co)polymerization of ethylene, as shown in the above analogs and prototypes inherent in the constitutional court, described in the patent of the Russian Federation No. 2177954 and containing UCC, upon receipt of which are used as precursors and oxide catalytically active metal (chromium), and modifying oxides (e.g. alumina) inorganic compounds of these metals, particularly their hydrated nitrates, i.e. connect the tion, radically different in their chemical nature of the used for this purpose according to the present method of organic derivatives of chromium and aluminum. The use according to the claimed method alkoxyalkane the above specific composition to obtain any catalysts or catalytic systems (co)polymerization of ethylene previously not been known; the substance of this type is used as a binder suspensions for the manufacture of ceramic molds for investment casting [RF patent №2082535, MKI622 With 1/06, 1/16, publ. 1997].

Third, used according to the claimed method termovosstanovleniyu activation of the UCC in the presence of carbon monoxide according to the known sources of information could lead to reduced activity of the UCC and, accordingly, the COP with its use. This follows both from the data of the above patent and prototype - that the highest activity for 1 h copolymerization has the double CC on the RF patent №2177954, including UCC, subjected to oxidative activation and containing chromium in the form of CR6+(compared to the COP, including the UCC with the recovered chromium in the form of CR2+), and the corresponding data of U.S. patent No. 5543376. According to the experiments 203 and 204 table 2 of example 2 of this U.S. patent, the COP on the basis of the UCC on the media - alumi state, containing 2 wt.% SG in the form of CR6+and SG(C5H5)2adsorbed on the UCC in the amount of 0.31 wt.%, provides in the process of suspension polymerization of ethylene in isobutane for 1 h output 2740 g HDPE/g KC· h, and when the content in the composition of the UCC same amount of chromium, but in regenerated form (CR2+), and adsorbirovannoi on UCC of chromocene in the amount of 0.28 wt.% - 1400 g of HDPE/g KC· h at the same conditions of polymerization: Rtotal=39 at PH2=2.5 ATA, tSOP=95° and 2.8 ppm Al(C2H5)3(socializaton) isobutane. Thus, if not restored, the UCC provides the activity of CS, is equal to 70 g of HDPE/g KC· h· at, then restored only 36 g of HDPE/g KC· h· at, i.e. almost 2 times lower.

High catalytic activity of the double CC on the basis of UCC obtained by the claimed method, which continues for a long time copolymerization, probably, is provided by forming a part of the UCC chromiferous active centers (AOC), a more stable during long-term operation in the presence hromitovogo catalyst, compared to AC ocenography catalysts of the same purposes, obtained by known methods. This catalytic property may be due to the specific ligand is environment AC - the surface fluorine-containing groups and molecules of aluminum oxide. These fluorine-containing group formed by the interaction of surface hydroxyl groups of the carrier of silicon dioxide in the form of silica gel with fluoride and hydrogen fluoride of silicon, formed by thermal decomposition of ammonium hexafluorosilicate at the stage of drying media (decomposition temperature (NH4)2SiF6is at atmospheric pressure of about 320° [Chemical encyclopedia / CH. edit Ilonen. - M.: Owls. day., 1988, vol. 1, p.153]; the formation of a fluorine-containing surface groups, this interaction is likely according to [Grated VA, L.A. Belyakova Chemical reaction involving the surface of the silica. - Kiev: Naukova Dumka, 1991. - 264 C.]). Aluminium oxide Al2O3as part of the UCC is formed by thermolysis used alkoxyalkane on stage thermal-oxidative activation (known [Korneev N.N., Dialects N.N., Tomashevsky MV Alyuminiiorganicheskikh connection. Obsorn. INF. Ser. "Organoelement compounds and their use". - M.: niitekhim, 1988, p.20] get Al2About3when thermolysis of alkoxyalkanols in oxygen-containing environment).

In accordance with the inventive method the drying medium is silicon dioxide is carried out in a fluidized bed in the presence of ammonium hexafluorosilicate at posto is authorized a temperature in the range of 330-400° C. the Absence of ammonium hexafluorosilicate at the stage of drying media UCC obtained by the claimed method, and, accordingly, the fluorine in the composition leads to lower long-term catalytic activity of the double CC on the basis of the UCC and resistance to cracking under stress synthesized on her HDPE (see our reference example 17). The lower limit of the constant temperature dryingcombined with fluoridation, media (330° (C) due to the above decomposition temperature of ammonium hexafluorosilicate; increaseabove 400° leads to lower long-term (average for 6 h) activity of this double COP and resistance to cracking under stress generated HDPE (see our reference example 18).

The decrease and increase of the constant temperature thermoactinomycetes activationrespectively below and above its limits - below 350° and above 390° upon receipt of the UCC - leads to the decrease of catalytic activity including its dual-COP (see our test cases 19 and 20).

UCC obtained by the present method shows high long-term activity and when it is not used in the composition of the double KS, and individually, however, synthesized while HDPE is not about lady high physical-mechanical indicators in particular its resistance to cracking under stress is only 535 h (see our reference example 21).

To prepare oxenkrug catalyst of the inventive method, as well as hromitovogo catalyst component with this UCC dual catalytic system, as media use silicon dioxide SiO2in the form of silica gel with the following structural characteristics: specific surface area (Sbeats)=220-350 m2/g; pore volume (Vthen) 1.3 to 1.9 cm /g, average particle size of 70-100 μm.

As a fluorinating agent of the silica gel carrier used by commercial powdered ammonium hexafluorosilicate (ammonium silicofluoride) (NH4)2SiF6the brand "H", a basic substance content not less than 99,0%by weight, produced by THE 6-09-1927-92.

All of the following examples illustrating the present invention, drying of the silica gel carrier, combined with its fluoridation, as oxidative and termovosstanovleniyu product activation application dicyclopentadienyliron and alkoxyalkane on dried and fluorinated silica gel, carried out in a quartz column (the activator), equipped in the lower part of the porous plate to distribute the flow of gas and a pocket for thermocouple; this column was placed in a vertical muffle furnace.

Kacha is the firmness of the predecessors of chromium oxide SGAs and aluminum oxide Al 2About3as part of the UCC received saleemi way, using, respectively, dicyclopentadienyliron (chromatin) SG(C5H5)2produced in the form of ~5%solution in toluene (same toluene solution of chromocene used for cooking hromitovogo catalyst - the second component of the double CC), and alkoxylation General formula [Al(OR)n(OR')1-nO]mwhere R=C2H5or ISO-C3H7; R'=C6H9O2(radical acetoacetic ester as a chelating agent); n=0.6 or 0.7; m=2-5 (alkoxyalkane has oligomeric structure and represents a "set" of oligomeric molecules with the number of repeated units - Al(OR)n(OR')1-nO - within 2 to 5), produced in the form of ~35-40%solution in absolute ethanol or isopropanol in THE 6-02-1-644-90.

After application of these compounds chromium and aluminum on media spend drying the resulting product to remove the solvent, and then thermal-oxidative activation at a temperature of 450-750° C. At these temperatures in an oxidizing atmosphere, the formation of oxides of chromium and aluminum with simultaneous separation of the oxidation of the organic component of the applied compounds of carbon dioxide gas CO2and water, i.e. practically harmless products is tov. In the subsequent thermoactinomycetes activation of the catalytic product, as in the commonly used methods thermoactinomycetes activation is carbon monoxide, which is a far less harmful substance (MPCSS=3 mg/m3) [Besplatno G.P., moles Y.A. Maximum permissible concentrations of chemical substances in the environment. - L.: Chemistry, 1985, p.71) compared to nitrogen dioxide NO2(MPCSSas already mentioned, is 0.04 mg/m3)produced during oxidative activation upon receipt of the UCC by the RF patent №2177954.

Applying chromocene and alkoxyalkane taken in the form of the solution, dried and fluorinated silica gel produced in the environment of isopentane (used solutions of chromium compounds and soluble aluminum in it) in a metal reactor with a volume of 0.2 l with built-in lower part of the cermet filter to remove solvent and equipped with an electromagnetic stirrer drive and a jacket for heating. In the same reactor are drying the obtained product.

Applied ocenography the catalyst obtained by the claimed method may be characterized by the General formula CrO/SiO2F· Al2About3; it contains in its composition, according to the analytical analyses of 1.2-2.2 wt.% SG, 0.5 and 0.9 wt.% F and 2,94,6 wt.% Al (analyses on the content of SG performed using volumetric titration, the content of F - method of ionometry using F-selective electrode, the contents of Al by atomic absorption spectrophotometry), which corresponds to the content in the catalyst of 1.6-2.9 wt.% SGAs, 0.5 and 0.9 wt.% F and 5.5 to 8.9 wt.% Al2O3.

Applied chromitovy the catalyst used in conjunction with applied UCC obtained by the claimed method, comprising double CA - the catalyst composition Cr(C5H5)2/SiO2get a bearing on termoaktivirovannye in a stream of dry air at constant temperature in the range from 600 to 800° media - silica gel chromocene of its hydrocarbon solution, followed by removal of solvent and drying of the obtained catalyst, which is then stored in a nitrogen atmosphere. The chromium content in cooked applied CCK is 1-2 wt.%. As applied hromitovogo catalyst composition of this COP can be used widely used in the industrial production of HDPE gas-phase method applied chromitovy catalyst "S-9" (composition Cr(C5H5)2/SiO2), developed by the company Union Carbide Corp. [U.S. patent No. 3709853, MKI 08 F 1/74, 3/06, publ. 1973].

In the Council's composition, including the UCC, obtained by the claimed method, it is preferable to use the marked UCC and CCK in such quantities that the mass ratio of SG(C5 H5)2/SGAs was 0.81-1,43; however, this ratio may be greater, namely from 0.50 to 1.70.

The effect of preserving for a long time copolymerization of ethylene catalytic activity of the double CC on the basis of the UCC received saleemi way, is most evident in the gas-phase process in the industrial production of HDPE is carried out within 4-8 hours This COP can also be used in the suspension process synthesis HDPE occurring 1-2 hours, in which she shows high activity (172-185 g HDPE/g KC· h· at).

The copolymerization of ethylene with α -olefins (butene-1, hexene-1 and others) on this catalytic system preferably carried out at a temperature of 40-110° and pressure of 1-50 at in suspension or gas-phase modes.

The molecular mass (MM) synthesized by the claimed method PEND characterized indirectly by the values of the TPP, as well as regulate the density ratio caused oxenkrug and hromitovogo catalysts in the composition of the catalytic system; in addition, MM (MFR) is adjusted by changing the constant temperature of thermal-oxidative activationupon preparation of supported UCC and constant temperature activation of the carrier of silica gel in the preparation of supported CCK, as well as the change in temperature is tours copolymerization, the partial pressure of ethylene, an introduction to the polymerization zone hydrogen and variation of its concentration; the density of HDPE also govern the change of the composition of the monomer mixture during the copolymerization of ethylene.

In the examples of the present invention the synthesis of HDPE, namely the copolymerization of ethylene with α -olefins in suspension or gas-phase modes, carried out in a reactor with a volume of 1.5 liters, equipped with a magnetic agitator and a jacket for heating.

Characteristics and properties of the resulting HDPE is determined as follows:

1. Density (ρ ) at a temperature of 20° - GOST 15139-69.

2. The melt flow index (MFR) at a temperature of 190° and With loads of 2.16 kg and 21.6 kg according to GOST 11645-73.

3. Yield strength tensile (σt) and elongation at break (εp) - according to GOST 11262-80.

4. Resistance to cracking under stress - according to GOST 13518-68.

All of these characteristics and properties determined on samples of HDPE, homogenised after copolymerization synthesis by mixing in the melt at a combined lab machine model YE-120, 669 (rollers) with multiple turning 90 degrees to cut the sheeting cloth (not less than 30 times).

The following examples illustrate the present invention.

Example 1

1. Getting OK ignoramous catalyst

In the activator download 17.0 g of silica gel SiO2(Sbeats=315 m2/g, Vthen=1,82 cm3/g) and 2.16 g of ammonium hexafluorosilicate (NH4)2SiF6and conduct drying and fluoridation media in conditions of fluidization purified nitrogen in the following temperature-time mode: heating up to 100° 1 h, heating from 100 to 200° 3 hours, heated from 200 to 330° 7 h exposure at 330° 2 h, cooled to room temperature 3 tsp Dried fluorinated silica gel in an amount of 15.6 g load in a stream of nitrogen in a reactor with a volume of 0.2 l (described above), served him in 0.1 l of purified and drained isopentane, load 1.0 g of chromocene SG(C5H5)2(predecessor of chromium oxide) in the form of a 5%solution in toluene and stirred for 13 hours at a temperature of 35° C. Then the solvent is removed by filtration and washed the resulting carrier with printed chromocene for 1 h in fresh isopentane (0.05 l), which after washing the filter.

Next to the reactor again serves cleaned and dried isopentane (0.1 l) and when running the mixer gradually (within 10 min) load 4.0 g alkoxyalkane [Al(Oi-C3H7)for 0.6(OS6H9O2)for 0.4O]2-5(as 40%solution in isopropanol) is added and stirred for 13 hours at a temperature of 35° C. Then the solvent is removed of ispar is observed with increasing temperature to 100-120° With continued stirring and dried the product at this temperature in a stream of nitrogen to a dry state within 4 hours

Then the resulting product (in the amount of 20.1 g) is subjected to thermal-oxidative activation in the fluidized bed in a stream of dry air, raising the temperature in the activator to 600° With speeds of up to 100° C/h, and for 10 h attnoaNext, the catalytic product is cooled to 370° replace the dry air purified nitrogen and feeding dry carbon monoxide in a stream of nitrogen to the content of 13-15% vol. CO in the gas mixture CO/N2spend termovosstanovleniyu activation of the catalytic product for 3 h atAfter this stop filing WITH, maintain the catalyst in a stream of purified nitrogen for 2 h at 370° S, and then cooled to room temperature. The catalyst (in an amount of 16.9 g) stored in a nitrogen atmosphere; the results of the analyses it contains 1.7 wt.% SG, 0.7 wt.% F and 3.0 wt.% Al, which corresponds to the content of 2.2 wt.% SG, 0.7 wt.% F and 5.7 wt.% Al2About3.

2. The composition used catalytic system

As the UCC as part of the COP for the synthesis of a copolymer of ethylene using the applied catalyst obtained as described above.

As applied hromitovogo catalysis the Torah as part of the COP for the synthesis of a copolymer of ethylene used industrial catalyst "S-9", media (SiO2) which are activated in a stream of dry air for 4 h at a constant temperature600° C. the Catalyst contains 1.8 wt.% SG.

The catalytic system is formed directly in the polymerization reactor by mixing batches of these caused UCC (0,022 g) and CCK (0,009 g). The mass ratio of SG(C5H5)2to SGAs in KS is 1,17. The total mass of the COP is 0,031,

3. Suspension copolymerization of ethylene with hexene-1

The copolymerization of ethylene with hexene-1 is carried out in the environment, clean and dry isopentane (0.75 l)using the above COP. The number loaded into the reactor prior to the copolymerization of 1-hexene is 25 ml (16,8 g). The copolymerization process is carried out at a temperature of 95° C, partial pressure of hydrogen of 2.5 and at total pressure of 35 ATA, supported by feeding ethylene. The copolymerization time (τSOP) is 1 o'clock Get 201 g of HDPE (copolymer of ethylene with hexene-1).

Conditions for obtaining the UCC and characteristics of the COP on its basis, the conditions of the copolymerization of ethylene with α -olefin, and the output of HDPE and properties of the synthesized HDPE in example 1 and all the following examples are given in tables 1, 2 and 3, respectively.

Example 2

1. Getting oxenkrug catalyst

Applied UCC receive the services which were the same conditions of example 1.

2. The composition used catalytic system

As UCC and CCK in the composition of the constitutional court apply the same applied catalysts as in example 1, using sample: UCC 0.025 g, CCK 0,012 g; the mass ratio of SG(C5H5)2/CDF equal to 1.37. The total mass of the COP is 0,037,

3. Suspension copolymerization of ethylene with hexene-1

The copolymerization of ethylene with hexene-1 is carried out in the conditions of example 1, but using the COP in this example, the number of downloaded hexene-1 is 20 ml (13.5 g). Get 223 g PEND.

Example 3

1. Getting oxenkrug catalyst

Applied UCC get in conditions analogous to example 1.

2. The composition used catalytic system

As UCC and CCK in the composition of the constitutional court apply the same applied catalysts as in example 1, using sample: UCC or 0.027 g, CCK to 0.011 g; the mass ratio of SG(C5H5)2/SGAs is 1,17. The total mass of the COP is 0.038,

3. Gas-phase copolymerization of ethylene with hexene-1

The copolymerization of ethylene with hexene-1 is carried out in the conditions of example 1, but using CC on this example, and in the absence of isopentane, i.e. in-phase mode; the number of downloaded hexene-1 is 10 ml (of 6.73 g). The copolymerization process is carried out at a temperature of 105° C, partial pressure of hydrogen is 0.5 and at a total pressure of 12 at supported by feeding ethylene. The copolymerization time is 1 o'clock Obtain 109 g PEND.

Example 4

1. Getting oxenkrug catalyst

Applied UCC get in conditions analogous to example 1.

2. The composition used catalytic system

As UCC and CCK in the composition of the constitutional court apply the same applied catalysts as in example 1, using sample: UCC 0,007 g, CCK 0.003 g; the mass ratio of SG(C5H5)2/CDF equal to 1.23. The total mass of the COP is 0,010,

3. Gas-phase copolymerization of ethylene with hexene-1.

The copolymerization of ethylene with hexene-1 is carried out in the conditions of example 3, but using CC on this example, and during the time of copolymerization equal to 6 o'clock Obtain 142 g PEND.

Example 5

1. Getting oxenkrug catalyst

Applied UCC get in conditions analogous to example 1.

2. The composition used catalytic system

As UCC and CCK in the composition of the constitutional court apply the same applied catalysts as in example 1, using sample: UCC 0,030 g, CCK 0,012 g; the mass ratio of SG(C5H5)2/CDF equal to 1.15. The total mass of the COP is 0,042,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene is carried out in the conditions of example 3, but using CC on this example, and instead of hexene-1 as is the co monomer of ethylene using butene-1. The molar ratio of the comonomers in their gas mixture With4H8/S2H4equal to 0.03. The copolymerization time is 1 o'clock Obtain 130 g of HDPE (copolymer of ethylene with butene-1).

Example 6

1. Getting oxenkrug catalyst

Applied UCC get in conditions analogous to example 1.

2. The composition used catalytic system

As UCC and CCK in the composition of the constitutional court apply the same applied catalysts as in example 1, using sample: UCC 0.008 g, CCK 0.003 g; the mass ratio of SG(C5H5)2/SGAs is of 1.07. The total mass of the COP is to 0.011,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Get 165 g PEND.

Example 7

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1, but as a solution of the aluminium compound used 40%solution alkoxyalkane [Al(Oi-C3H7)0,7(OS6H9O2)for 0.3Oh]2-5in absolute isopropanol, and load 15 g of the solution (6.0 g alkoxyalkane). The resulting catalyst contains test results 1.6 wt.% SG, 0.7 wt.% F and 4.7 wt.% Al, that is correspond to the content of 2.1 wt.% SGAs 0.7 wt.% F and 8.9 wt.% Al2About3.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 1, using sample: UCC 0.008 g, CCK 0.003 g; the mass ratio of Cr(C5H5)2/CrO is of 1.07. The total mass of the COP is to 0.011,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Get 172 g PEND.

Example 8

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1, but as a solution of aluminum compounds used by 36%solution alkoxyalkane [Al(OC2H5)for 0.6(OS6H9O2)for 0.4O]2-5in absolute ethanol, and load 10 g of the solution (3.6 g alkoxyalkane). The resulting catalyst contains the results of analyses of 1.7 wt.% SG, 0.7 wt.% F and 2.9 wt.% Al, which corresponds to the content of 2.2 wt.% SGAs, 0.7 wt.% F and 5.5 wt.% Al2About3.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - t the same applied catalyst, as in example 1, using sample: UCC to 0.011 g, CCK 0.004 g; the mass ratio of SG(C5H5)2/CDF equal to 1.04 million. The total mass of the COP is 0,015,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Get 217 g PEND.

Example 9

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1, but as a solution of aluminum compounds used by 36%solution alkoxyalkane [Al(OC2H5)0,7(OS6H9O2)for 0.3Oh]2-5in absolute ethanol, and the load 15 g of the solution (5,4 g alkoxyalkane). The resulting catalyst contains test results 1.6 wt.% SG, 0.7 wt.% F and 4.6 wt.% Al, which corresponds to the content of 2.1 wt.% SGAs, 0.7 wt.% F and 8.7 wt.% Al2About3.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 1, using sample: UCC 0,010 g, CCK 0.004 g; the mass ratio of SG(C5H5)2/CDF equal to 1.20. The total mass of the constitutional court is of 0.014,

3. Gas-phase copolymerization this is Lena with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Get 211 g PEND.

Example 10

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1, but the preliminary drying of silicon dioxide is carried out at a constant temperature equal to 400° C. the Composition of the obtained catalyst similar to the catalyst composition of example 1.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 1, using sample: UCC 0.008 g, CCK 0.003 g; the mass ratio of SG(C5H5)2/SGAs is of 1.07. The total mass of the COP is to 0.011,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Obtain 158 g PEND.

Example 11

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1, but termovosstanovleniyu catalytic activation of the product is carried out at essentially the first temperature to 350° C. the Composition of the obtained catalyst similar to the catalyst composition of example 1.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 1, using sample: UCC to 0.011 g, CCK 0.004 g; the mass ratio of SG(C5H5)2/CDF equal to 1.04 million. The total mass of the COP is 0,015,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Get 219 g PEND.

Example 12

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1, but termovosstanovleniyu catalytic activation of the product is carried out at a constant temperature of 390° C. the Composition of the obtained catalyst similar to the catalyst composition of example 1.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 1, using sample: UCC to 0.011 g, CCK 0.004 g; the mass ratio of SG(C5H5)2/CDF equal to 1.04 million. The total mass of the COP is 0.05,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Get 204 g PEND.

Example 13

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1, but during the preliminary drying of the carrier - silicon dioxide - activator download 1.54 g of ammonium hexafluorosilicate (NH4)2SiF6when applied to the dried silica gel compounds of chromium was charged to the reactor 14 g of a 5%solution of chromocene SG(C5H5)2in toluene (0.7 g chromocene), and thermal-oxidative activation of the resulting product is carried out at a constant temperature to 450° C. the resulting catalyst contains the results of analyses of 1.2 wt.% CR, 0.5 wt.% F and 3.1 wt.% Al, which corresponds to the content of 1.6 wt.% SGAs, 0.5 wt.% F and 5.9 wt.% AL2About3.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 1, using sample: UCC to 0.011 g, CCK 0.004 g; the mass ratio of SG(C5H5)2/SGAs is 1,43. The total mass of the COP is 0,015,

3. Gas-phase with polymerizate of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Obtain 183 g PEND.

Example 14

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1, but during the preliminary drying of the carrier - silicon dioxide - activator download 3.03 g ammonium hexafluorosilicate (NH4)2SiF6when applied to the dried silica gel compounds of chromium was charged to the reactor 26 g of a 5%solution of chromocene SG(C5H5)2in toluene (1.3 g of chromocene), and thermal-oxidative activation of the resulting product is carried out at a constant temperature of 750° C. the resulting catalyst contains the results of analyses of 2.2 wt.% SG, 0.9 wt.% F and 2.9 wt.% Al, which corresponds to the content of 2.9 wt.% SGAs, 0.9 wt.% F and 5.5 wt.% Al2About3.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 1, using sample: UCC 0.008 g, CCK 0.003 g; the mass ratio of SG(C5H5)2/SGAs is 0,81. The total mass of the COP is to 0.011,

3. Gas-phase copolymerization of ethylene with butene-1

Copolymerizate the ethylene with butene-1 is carried out in the conditions of example 5, but using CC on this example, and during the time of copolymerization equal to 6 o'clock Get 178 g PEND.

Example 15

1. Getting oxenkrug catalyst

Applied UCC get in conditions analogous to example 1.

2. The composition used catalytic system

As the UCC as part of the COP used the same applied catalyst as in example 1.

As applied hromitovogo catalyst used industrial catalyst "S-9", medium (SiO2) which are activated in a stream of dry air for 4 h at a constant temperature equal to 700° C. the Catalyst contains 1.7 wt.% SG.

Use sample: UCC 0,009 g, CCK 0.004 g; the mass ratio of SG(C5H5)2/CDF equal to 1.20. The total mass of the COP is 0,013 g

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene is carried out in the conditions of example 5, but using the COP in this example, when the molar ratio of the comonomers in their gas mixture C4H8/C2H4equal to 0.05, the temperature is 100° and during the time of copolymerization equal to 6 o'clock Get 191 g PEND.

Example 16

1. Getting oxenkrug catalyst

Applied UCC get in conditions analogous to example 1.

2. The composition used catalytic system

As UCC amend the t same applied catalyst, as in example 1, as CCK - same-deposited catalyst as in example 15, using a sample: UCC 0,009 g, CCK 0.004 g; the mass ratio of Cr(C5H5)2/CrO equal to 1.20. The total mass of the COP is 0,013 g

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene is carried out in the conditions of example 5, but using the COP in this example, at a temperature of 110° C, partial pressure of hydrogen to 1.0 at and during the time of copolymerization equal to 6 o'clock Get 186 g PEND.

Example 17 (control)

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1, but prior to the drying medium is silicon dioxide is carried out in the absence of ammonium hexafluorosilicate (NH4)2SiF6. The resulting catalyst contains the results of analyses of 1.7 wt.% SG, 3.0 wt.% Al, which corresponds to the content of 2.2 wt.% SGAs and 5.7 wt.% Al2About3.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 1, using sample: UCC to 0.011 g, CCK 0.004 g; the mass ratio of SG(C5H5)2/CDF equal to 1.04 million. The total mass of the COP is 0,015,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Get 137g PEND.

Example 18 (control)

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1, but prior to the drying medium is silicon dioxide is carried out at a constant temperature to 450° C. the resulting catalyst contains the results of analyses of 1.7 wt.% CR, 0.5 wt.% F and 3.0 wt.% Al, which corresponds to the content of 2.2 wt.% SGAs, 0.4 wt.% F and 5.7 wt.% Al2About3.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 1, using sample: UCC to 0.011 g, CCK 0.004 g; the mass ratio of SG(C5H5)2/CDF equal to 1.04 million. The total mass of the COP is 0,015,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Get 163 spend.

Example 19 (control)

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared in the conditions, Ana is ulichnyh the conditions of example 1, but termovosstanovleniyu catalytic activation of the product is carried out at a constant temperature 330° C. the Composition of the obtained catalyst similar to the catalyst composition of example 1.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 1, using sample: UCC to 0.011 g, CCK 0.004 g; the mass ratio of SG(C5H5)2/CDF equal to 1.04 million. The total mass of the COP is 0,015,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Get 160 g PEND.

Example 20 (control)

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1, but termovosstanovleniyu catalytic activation of the product is carried out at a constant temperature of 410° C. the Composition of the obtained catalyst similar to the catalyst composition of example 1.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 1, ISOE is isua sample: UCC to 0.011 g, CCK 0.004 g; the mass ratio of SG(C5H5)2/CDF equal to 1.04 million. The total mass of the COP is 0,015,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, and during the time of copolymerization equal to 6 o'clock Obtain 149 g PEND.

Example 21 (control)

1. Getting oxenkrug catalyst

Applied ocenography the catalyst was prepared under conditions similar to the conditions of example 1.

2. Used catalyst

Apply only one of the marked UCC is the same as in example 1 (without CCK); linkage UCC is 0,010,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the catalyst according to this example, and during the time of copolymerization equal to 6 o'clock Get 191 g PEND.

Example 22 (control, prototype)

1. Getting oxenkrug catalyst

10.0 g of silica gel - SiO2(Sbeats=305 m2/, Stop=1,80 cm3/g), dried at 200° With the flow of the nitrogen load in the reactor, served him in 0.1 l of a solution prepared by dissolving in a mixture of 0.02 l of ethanol and 0.08 l of acetone (volume ratio 1:4) 1,91 g nonahydrate nitrate chromium (III) Cr(NO3)3·9H2O 7,94 g nonahydrate neath the ATA aluminum Al(NO 3)3·9H2O, 1,53 g of uranyl nitrate zinc Zn(NO3)2·6H2O, and stirred at 20° 4 hours Then the solvent is removed by evaporation at elevated temperature to 100° with continued stirring and dried the product at this temperature in a stream of nitrogen for 4 hours

Next, the resulting product (19.6 g) is loaded into the activator and activate in the fluidized bed in a stream of dry air, raising the temperature in the activator from 100 to 500° With speeds of up to 100° C/h, i.e. within 4 h, and 4 h activate the product at tnoa=500° C. the resulting catalyst is cooled in a stream of dry air to a temperature of 200° and replace the air with nitrogen, the flow of which is cooled catalyst to room temperature. The resulting catalyst (12.0 g) stored in a nitrogen atmosphere; the results of the analyses it contains about 2.1 wt.% Cr, 4.75 wt.% Al and 2.8 wt.% Zn, which corresponds to the content of 4.0 wt.% CrO3, to 9.0 wt.% Al2O3and 3.5 wt.% ZnO.

2. The composition used catalytic system

As the UCC applied applied catalyst obtained according to this example, as CCK - same-deposited catalyst as in example 15, using a sample: UCC 0.015 g, CCK 0.008 g; the mass ratio of Cr(C5H5)2/CrO3well 0,79. The total weight is and KS is 0,023,

3. Gas-phase copolymerization of ethylene with butene-1

The copolymerization of ethylene with butene-1 is carried out in the conditions of example 5, but using the COP in this example, at a temperature of 105° and during the time of copolymerization equal to 6 o'clock Get 131 g PEND.

As can be seen from the data presented above and in tables 1-3, the inventive method provides for obtaining applied the UCC, with high long-term polymerization activity, namely the average activity for 6 h gas-phase copolymerization of ethylene with butene-1, is equal to 204 g of HDPE/g cat· h· at (see our reference sample No. 21), which implies a high long-term (average for 6 h) activity double KS, including the UCC and applied CCK media - silicon dioxide constituting 169-225 g HDPE/g COP· h· at. Specified long-term activity of the COP using the UCC, obtained by the claimed method, 2.1-2.8 times higher long-term activity of the constitutional court of the prototype. The activity of CS-based UCC claimed method for 1 h copolymerization (172-258 g HDPE/g KC· h· at) 2.5-2.8 times higher than the activity of the constitutional court on the known analogues and 15-20% higher than the activity of the constitutional court of the prototype. Increased activity (especially long-term activity that is most relevant for gas-phase polymerization process characterized by long times is m stay catalyst particles in the reaction zone), the COP can reduce the specific consumption of its components per 1 ton of produced goods (HDPE), therefore, to increase the efficiency of the synthesis process, which is especially important for large-scale production, which is the industrial production of HDPE.

Obtained using the CC, including the UCC by the present method, the HDPE has an optimal range of physical and mechanical properties: density 0,950-0,956 g/cm3characterized by high resistance to cracking under stress (>1000 h), the yield strength tensile (24,0-of 25.6 MPa), elongation at break (620-825%). This HDPE, having a wide DFID (PTR21,6/VKT2,16=112-242, see table 3), the most promising for fabrication by extrusion packaging films and high strength, crack resistant pipes for transporting natural gas.

The method of obtaining oxenkrug catalyst on an inorganic carrier - dual component catalyst system for the copolymerization of ethylene, containing also applied chromitovy catalyst, including pre-drying of the carrier - silicon dioxide coating on the dried carrier compounds chromium and aluminum from their solutions in organic solvent, removing the solvent, drying the resulting product and its posleduyushe thermal-oxidative activation in a stream of dry air at constant temperature in the range from 450 to 750° , Characterized in that the solution of the aluminium compound used solution alkoxyalkane General formula

[Al(OR)n(OR')1-nO]m,

where R=C2H5or ISO-C3H7;

R’=C6H9O2,

n=0.6 or 0.7;

m=2-5,

in absolute lower aliphatic alcohol as a solution of the compound of chromium - solution dicyclopentadienyliron in toluene, and the preliminary drying of the carrier of silicon dioxide is carried out in a fluidized bed in the presence of ammonium hexafluorosilicate at a constant temperature in the range of 330-400°and after thermo-oxidative activation of conduct termovosstanovleniyu activation of the catalytic product in the stream of the mixture purged with dry nitrogen monoxide at a constant temperature in the range from 350 to 390°C.



 

Same patents:

The invention relates to the field of catalytic systems for the polymerization or copolymerization of cycloolefins norbornene-type

The invention relates to a method for producing polyolefins, the molecules of which contain short branched side chains by polymerization of alpha-olefins

The invention relates to a continuous method of gas-phase fluidized to obtain homopolymerization and copolymerizate ethylene with density d from 0.89 to 0.97 g/cm3

The invention relates to a method of polymerization, which is that the catalyst, inhibitor of polymerization, ethylene and possibly comonomer olefins are in contact under conditions of polymerization, the catalyst comprises chromium oxide, titanium oxide and refractory inorganic oxide, the polymerization retarder selected from the group comprising alcohols, aldehydes, ketones, esters, organic acids and their mixtures

The invention relates to a copolymer of ethylene with at least one alpha-olefin obtained by using a solid catalytic material based on chromium oxide deposited on a homogeneous amorphous media, and with the turnover rate HLMI, expressed in g/10 min, the amount of alpha-olefin Q, expressed in g of alpha-olefin per 1 kg of the copolymer, of the standard volumetric mass (COM), expressed in kg/m3and at least equal (952,75+5,40lg HLMI-0,79Q), and the relatively wide distribution of molecular masses

The invention relates to catalysts for (co)polymerization of ethylene containing chromium trioxide deposited on a solid inorganic oxide carrier of nature, i.e

FIELD: powder metallurgy; method of impregnation by a metal(of VIII group) of a molecular sieve extrudate with cementing material with the help of ion exchange with an aqueous solution of metal salt of VIII group.

SUBSTANCE: the invention presents a method of impregnation by metal of VIII group of an extrudate of a molecular sieve with cementing material, in which the cementing material represents a refractory oxidic material with a low acidity, practically free of aluminum oxide, using: a) impregnation of porous volume of an extrudate of a molecular sieve with cementing material with an aqueous solution of nitrate of the corresponding metal of VIII group with pH from 3.5 up to 7, in which the molar ratio between cations of a metal of VIII group in a solution and a number of centers of the adsorption available in the extrudate, is equal to or exceeds 1; b) drying of the produced at the stage a) extrudate of the molecular sieve with the cementing material. The technical result is good distribution of the metal and a short period of drying.

EFFECT: the invention ensures good distribution of the metal and a short period of drying.

9 cl, 1 tbl, 4 ex

FIELD: alternate fuel manufacture catalysts.

SUBSTANCE: invention relates to generation of synthesis gas employed in large-scale chemical processes such as synthesis of ammonia, methanol, higher alcohols and aldehydes, in Fischer-Tropsch process, and the like, as reducing gas in ferrous and nonferrous metallurgy, metalworking, and on gas emission detoxification plants. Synthesis gas is obtained via catalytic conversion of mixture containing hydrocarbon or hydrocarbon mixture and oxygen-containing component. Catalyst is a complex composite containing mixed oxide, simple oxide, transition and/or precious element. Catalyst comprises metal-based carrier representing either layered ceramics-metal material containing nonporous or low-porosity oxide coating, ratio of thickness of metallic base to that of above-mentioned oxide coating ranging from 10:1 to 1:5, or ceramics-metal material containing nonporous or low-porosity oxide coating and high-porosity oxide layer, ratio of thickness of metallic base to that of nonporous or low-porosity oxide coating ranging from 10:1 to 1:5 and ratio of metallic base thickness to that of high-porosity oxide layer from 1:10 to 1:5. Catalyst is prepared by applying active components onto carrier followed by drying and calcination.

EFFECT: increased heat resistance and efficiency of catalyst at short contact thereof with reaction mixture.

13 cl, 2 tbl, 17 ex

FIELD: chemical industry, in particular two-component heterogeneous immobilized catalyst for ethylene polymerization.

SUBSTANCE: claimed catalyst includes alumina, mixture of transition metal complexes with nitrogen skeleton ligands (e.g., iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex). According the first embodiment catalyst is prepared by application of homogeneous mixture of transition metal complexes onto substrate. iron chloride bis-(imino)pyridil complex and nickel bromide bis-(imino)acetonaphthyl complex (or vise versa) are alternately applied onto substrate. According the third embodiment catalyst is obtained by mixing of complexes individually applied onto substrate. Method for polyethylene producing by using catalyst of present invention also is disclosed.

EFFECT: catalyst for producing polyethylene with various molecular weights, including short chain branches, from single ethylene as starting material.

7 cl, 5 tbl, 27 ex

FIELD: alternative fuel production and catalysts.

SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.

EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.

6 cl, 2 tbl, 16 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of catalyst comprises applying palladium compound onto silica cloth and heat treatment. Palladium compound is applied by circulation of toluene or aqueous palladium acetate solution through fixed carrier bed until palladium content achieved 0.01 to 0.5%. Palladium is introduced into cloth in dozed mode at velocity preferably between 0.1 and 5.9 mg Pd/h per 1 g catalyst. Heat treatment includes drying at temperature not higher than 150oC under nitrogen or in air and calcination in air or nitrogen-hydrogen mixture flow at temperature not higher than 450oC. Original silica cloth can be modified with 0.6 to 6.5% alumina. Palladium is uniformly distributed in silica cloth and has particle size preferably no larger than 15 Å. Invention can be used in treatment of industrial gas emissions and automobile exhaust to remove hydrocarbons.

EFFECT: deepened oxidation of hydrocarbons.

5 cl, 1 tbl, 4 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of catalyst comprises two-step impregnation of preliminarily calcined carrier with first ammonium heptamolybdate solution and then, after intermediate heat treatment at 100-200°C, with cobalt and/or nickel nitrate solution followed by final heat treatment including drying at 100-200°C and calcination at 400-650°C. Catalyst contains 3.0-25.0% MoO3, 1.0-8.0% CoO and/or NiO on carrier: alumina, silica, or titanium oxide.

EFFECT: enhanced hydrodesulfurization and hydrogenation activities allowing involvement of feedstock with high contents of sulfur and unsaturated hydrocarbons, in particular in production of environmentally acceptable motor fuels.

3 cl, 4 tbl, 13 ex

FIELD: supported catalysts.

SUBSTANCE: invention claims a method for preparation of catalyst using precious or group VIII metal, which comprises treatment of carrier and impregnation thereof with salt of indicated metal performed at working pressure and temperature over a period of time equal to or longer than time corresponding most loss of catalyst metal. According to invention, treated carrier is first washed with steam condensate to entirely remove ions or particles of substances constituted reaction mixture, whereupon carrier is dried at 110-130oC to residual moisture no higher than 1%.

EFFECT: achieved additional chemical activation of catalyst, reduced loss of precious metal from surface of carrier, and considerably increased lifetime.

5 cl, 9 ex

FIELD: petrochemical synthesis catalysts.

SUBSTANCE: invention discloses a method for preparation of palladium catalyst comprising impregnation of alumina carrier with palladium chloride solution in presence of aqueous hydrochloric acid, treatment with reducing agent (hydrogen), washing with water, and drying, said carrier being preliminarily decoked exhausted catalyst containing alumina and group I and/or II, and/or VI, and/or VIII metals and subjected to washing with aqueous hydrochloric or nitric acid and then with water. Exhausted ethylene oxide production catalyst or methylphenylcarbinol dehydration catalysts can also be suitably used.

EFFECT: increased selectivity and activity of catalyst.

2 cl, 2 tbl, 21 ex

FIELD: petroleum processing catalysts.

SUBSTANCE: invention related to hydrofining of hydrocarbon mixtures with boiling range 35 to 250оС and containing no sulfur impurities provides catalytic composition containing β-zeolite, group VIII metal, group VI metal, and possibly one or more oxides as carrier. Catalyst is prepared either by impregnation of β-zeolite, simultaneously or consecutively, with groups VIII and VI metal salt solutions, or by mixing, or by using sol-gel technology.

EFFECT: increased isomerization activity of catalytic system at high degree of hydrocarbon conversion performed in a single stage.

40 cl, 2 tbl, 19 ex

Up!