The method of producing catalyst

 

(57) Abstract:

The invention relates to a method for producing a catalyst-type Ziegler-Natta based on the precipitation of vanadium compounds on MgCl2spherical media. Obtaining catalyst consists of interaction in the liquid hydrocarbon reducing vanadium substances taken from ORGANOMETALLIC substances soluble in the liquid hydrocarbon compound of vanadium containing at least one group of halogen and alkoxy group with media containing MgCl2free from Mg-C-organic compound and an electron donor, free from active hydrogen. The media consists of spherical particles with well-defined diameter and a narrow particle size distributions. The catalyst is particularly suitable for the production of gas-phase elastomeric copolymer of propylene. 5 C.p. f-crystals, 1 table.

The invention relates to the field of heterogeneous catalysis and concerns a method for obtaining a catalyst of the type Ziegler-Natta.

A method of obtaining a catalyst of the type Ziegler-Natta by precipitation of vanadium compounds in the liquid hydrocarbon solid carrier is magnesium dichloride having spherical particles with the structure Dmto srednecenovom diameter number Dnequal to 1.3 to 1.8; media-dichloride, magnesium contains electron donor, in particular isoamyl ether. The deposition is carried out by reaction of the recovery of vanadium compounds in the presence of the media without the addition of reducing substances. The reaction of the recovery is likely to begin spontaneously substances having the Mg-C bond, which are available in the media. The catalyst used in the production of polymers of ethylene, having a wide distribution of molecular weight. However, this process requires a large amount of vanadium compounds, but a small amount remains on the media. Usually requires washing of the catalyst to remove excess vanadium compounds, which remains on the carrier, and these operations are expensive and difficult due to the toxic and corrosive nature of vanadium compounds.

Found a production method of spherical catalyst is vanadium on the media of magnesium chloride, which avoids the above disadvantages. In particular, this method allows to obtain spherical vanadium-containing catalyst, which shows a lot of activity in the polymerization of olefins. This catalyst customerization in the gas phase. In this case, the catalyst allows directly the powder elastomeric propylene copolymer in the form of spherical and non-sticky particles, this powder has good fluidity and easy to apply.

The aim of the invention is a method of obtaining a catalyst with a high content of vanadium by the precipitation in the liquid hydrocarbon through the reaction of recovery on a spherical carrier-magnesium chloride.

This goal is achieved by the fact that the deposition is performed by the interaction in the liquid hydrocarbon reducing agent diethylformamide with soluble in the hydrocarbon compound of vanadium containing at least one halogen and one alkoxygroup, and solid media containing 84-95 mol. the magnesium dichloride, practically free from substances containing the link Mg-C, and 5-16 mol. vitaminology ether.

In accordance with the invention, upon receipt of the catalysts using a specific carrier is magnesium chloride. The carrier shall be no substances containing Mg-C bond, this means that the ratio of the number of Mg-C-bonds to the number of magnesium atoms should be less than 0.001. Therefore, the precipitation of vanadium compounds on the carrier of vanadia is carried out using a reducing agent, selected from ORGANOMETALLIC compounds, which react with the carrier-magnesium chloride and a compound of vanadium. The amazing aspect of this method is connected with the fact that the connection of vanadium associated with solid media without significant deposition except for the particles of the medium.

Media-magnesium chloride includes a relatively large number of organic compounds-electron donor D. This property contributes to the binding of a large number of vanadium compounds with a carrier and makes the catalyst more active in the polymerization or copolymerization of olefins. The media contains from 84 to 95 mol. of magnesium dichloride and from 5 to 16 mol. connections D. Preferably it contains from 80 to 95 mol. of magnesium dichloride and gives excellent vanadium-containing catalyst for polymerization of olefins. Excellent results are obtained in the manufacture of elastomeric propylene copolymers, when used media contains from 80 to 90 mol. of magnesium dichloride and from 10 to 16 mol. connections D.

Organic compound and an electron donor D is known as such or as a Lewis base. It is free from active hydrogen may be water, alcohol or phenol. For example, it is to choose from ethers, the thioethers, sulfones, sulfoxidov, phosphines, amines and amides. Preference is given to vitaminology ether.

It was found that the best results are achieved when the medium is homogeneous, i.e., the connection D are distributed uniformly across the particles of magnesium chloride from the core to the periphery, and not just on the periphery. As a result, to obtain the carrier of this type, it is recommended to use the method of deposition. In this case, the connection D is selected from substances, no reacts with the reagents used in the deposition. For example, compound E may be selected from esters of carboxylic acids, which react with the coupling of the Grignard reagent or magnetogenesis connections.

It was also found that the media provides high activity of the catalyst, able to withstand severe stress growth during the polymerization, when he has an amorphous structure, i.e. the structure, when the shape of crystallinity to a large extent or completely disappear. This particular form of media can be obtained by deposition carried out at a relatively precise terms.

Media differs in that it consists of spherical particles which have a mass-average of diaster, what is the ratio of mass-average diameter Dmto srednecenovom diameter Dnless than 2. More specifically, the size distribution of these particles can be very narrow, such that the ratio of Dm/Dnfrom 1.1 to 1.8, we can note the absence of particles with a diameter of more than 1.5 Dmor less than 0.6 Dm; the size distribution of particles can be determined by the fact that more than 90% by weight of particles of one portion have a size in the range Dm+10% Spherical particles are secondary particles, which are spherical in shape, the ratio of long axis to short is equal to or less than about 1.5, preferably less than 1.3.

The specific surface of particles of the medium may be from 20 to 100 m2/g (bet), preferably from 30 to 60 m2/g (bet) and a relative density of these particles may be approximately 1.2 and 2.1.

The carrier can be prepared by reaction of the compound dialkylamide with an organic chlorine compound in the presence of compound D electron donor. The selected connection diallylamine can be a substance of the formula R1MgR2where R1and R2the same or different alkyl radicals containing from 2 to 12 atoms uglerodsesola getting media. Selected organic chlorine compound is an alkyl chloride of the formula R3Cl, where R3secondary or preferably a tertiary alkyl radical containing from 3 to 12 carbon atoms. Used by the connection D of the electron donor is preferably an ether of formula R4OR5where R4and R5the same or different alkyl with 1-12 carbon atoms.

In addition, various reactive substances can be used to obtain the media under the following conditions:

the molar ratio R3Cl/R1MgR2may be from 0.1 to 2.5, preferably from 2 to 2.3.

the molar ratio D/R1MgR2from 0.1 to 1.2, preferably from 0.3 to 0.8.

The reaction between R1MgR2and R3Cl in the presence of compound D of the electron donor is precipitation, which is carried out by stirring in a liquid hydrocarbon. For the best media, especially characterized by the presence of a large number of connection D. an electron donor, it is recommended to carry out the deposition reaction at a relatively low temperature in the range from 10 to 50aboutC, preferably from 15 to 35aboutC. it is Further recommended that the response of precipitation to carry out W HY the formation of solids, in particular the penetration of a large number of compounds D and its uniform distribution in the formed carrier.

The method of producing the catalyst is in the deposition of vanadium compounds on a carrier of magnesium chloride in the liquid hydrocarbon. The liquid hydrocarbon may be one or more alkanes, such as n-hexane or n-heptane. Compound of vanadium is soluble in the liquid hydrocarbon substance. It is known that, in General, soluble in the liquid hydrocarbon vanadium compounds are those in which the valency of vanadium maximum, for example 4, or where the vanadium has a maximum value, for example 3.

Connection vanadium contains at least one halogen X and at least one alkoxygroup OR. It was noted, that allow to obtain elastomeric copolymers of propylene in the gas phase the catalysts that were obtained with the compound of vanadium, where the molar ratio X/OR from 0.05 to 20, preferably from 1 to 10. It was noted that with such catalysts it is possible to get directly in the gas phase non-adhesive elastomeric copolymer powder with good fluidity. It was also noted that the elastomeric propylene copolymer, obtained in this way, there is tons to meet one of the two formulas

V(OR)4-mXmor VO(OR)3-nXnwhere R is an alkyl radical containing 1-12 carbon atoms;

X halogen atom such as bromine or chlorine;

m is a whole or fractional number ranging from 0.2 to 3.8, preferably from 2 to 3.6;

n is an integer or fractional number ranging from 0.14 to 2.85, preferably from 1.5 to 2.7.

The connection of vanadium can be obtained by using a suitable mixture of halide, vanadium compounds of the formula VOX3and VX4with the vanadium alkoxide of the formula VO(OR)3or V(OR)4or a mixture of halide, vanadium compounds of the formula VOX3or VX4with alcohol of the formula ROH, where the groups X and R1have the specified values.

Of the halide of vanadium compounds are preferred vanadium tetrachloride or trichloride vanadium and vanadium alkoxides preferably tri-n-propoxide vanadium, triisopropoxide vanadium or Tetra-n-propoxide vanadium. The connection of vanadium can be obtained either prior to its use for the preparation of the catalyst or directly in the liquid hydrocarbon, which will take place in the deposition of the catalyst in the presence of the media.

The number of vanadium compounds used for the preparation of the catalyst depends on the desire is in, present in the media. The number of vanadium compounds used for the preparation of the catalyst, usually from 0.05 to 2, preferably from 0.1 to 1 mol per 1 mol of the magnesium dichloride carrier.

The method of producing catalyst consists of deposition of vanadium compounds on the media reaction to the recovery of vanadium from regenerating agent diethylaluminium. You can use a small amount of a reducing agent, if the gap of the catalyst into small particles during the polymerization can be avoided. Commonly used reducing agent during deposition in the amount of 0.05 to 1.5, preferably from 0.1 to 1 mol per 1 mol of the magnesium dichloride carrier. Further, the catalyst can be obtained in the presence of an additional amount of compound of the electron donor are identical to or different from that present in the media.

Associated with the media vanadium mainly located in the restored form. The deposition of the catalyst in the liquid hydrocarbon is carried out with the cooperation of the media connection vanadium and regenerating substance at a temperature which can be from 0 to 120aboutC, preferably from 50 to 90aboutC. reacting priblizitelbno. For example, regenerating substance and a compound of vanadium can be added simultaneously to a suspension of magnesium chloride media in the liquid hydrocarbon. Thus obtained mixture may be mixed with from 0.5 to 15 hours the Other way is by sequential addition of the reducing agent and vanadium compounds in any order to the suspension media of magnesium chloride. In particular, for increasing the number associated with the media vanadium preferably first reducing agent to enter into interaction with the suspension media of magnesium chloride, and then added to the suspension media connection vanadium. Although the main part of the used amount of vanadium compounds is associated with the carrier, the catalyst may be washed one or more times with a liquid hydrocarbon.

Rather amorphous structure of the medium is not changed during the preparation of the catalyst. Thus, the catalyst consists of particles, the physical properties are virtually identical to the properties of the particle source media. In particular, the catalyst consists of spherical particles with srednevekovym diameter from 10 to 100 μm, preferably from 20 to 50 μm and the grain size distribution, specific is the way to obtain due to the fact, most used vanadium compounds associated with the media. It was found that more than 80% and even more than 90% of the applied vanadium compounds in the process associated with the media. Another characteristic of the method is that the connection of vanadium is located evenly on the media, making the active catalyst during the polymerization. Compound of vanadium is distributed evenly on each particle of the medium from the core to the periphery. It was observed that the number of organic compounds D donor of electrons originally present in the media, is significantly reduced in the catalyst. From this we can conclude that the connection of vanadium may contact the carrier, displacing the connection D. it was Further noted that the catalyst includes a part of the reducing substances used during deposition, but in a modified form after the reaction of recovery. Thus obtained catalyst may contain 1 mol of magnesium dichloride from 0.05 to 2 mol of vanadium, 0.01 to 0.01 mol of the compounds of the donor electrons from 0.05 to 1 mol of the reducing substances in the form of a modified reaction recovery. Obtained in accordance with the invention, the catalyst can be used for Polk ethylene, propylene, 1-butylene, hexene, 4-methyl-1-penten Il 1-octene. It is particularly suitable for the production of elastomeric propylene copolymers, especially those containing from 30 to 70% by weight of propylene and from 70 to 30% by weight of ethylene and/or 1-butylene and possibly non-conjugate diene, for example, ethylidenenorbornene, 4-methyl-1,4 - hexadiene and 2-methyl-1,5-hexadien or 1,4-hexadiene. Elastomeric copolymers can be produced in the gas phase in a fluidized and/or mechanically mixed layer. The copolymerization reaction of propylene is carried out using the catalyst together with socialization selected from ORGANOMETALLIC compounds of a metal belonging to group I of the periodic table of the elements and preferably with an activator selected from halogenated hydrocarbons. The catalyst and socialization typically used in such proportions that the molar ratio of vanadium catalyst from 0.5 to 50. The copolymerization reaction can be carried out at a temperature of from about 0about60aboutWhen the total pressure of from 0.1 to 5 MPa. Obtained in accordance with the invention, the catalysts can be used directly or after having been subjected to surgery prior Aoda. The operation of pre-polymerization leads to an increase of the particle size of the catalyst, while maintaining the morphology of the latter. It is in the interaction of the catalyst and socializaton with one or more olefins. The reaction of the preliminary polymerization can be carried out while maintaining a suitable catalyst activity to obtain 10-500 g and preferably 30-250 g of the polyolefin in millimoles of vanadium. During the copolymerization reaction of propylene observed uniform development of liquid particles of the copolymer obtained elastomeric propylene copolymer consisting of a friction-free powder, which has good fluidity, high bulk density, typically 0.3-0.5 g/cm3. The copolymer has a relatively narrow distribution of molecular weight, characterized by the ratio of mass-average molecular mass Mwtosrednetsenovoj molecular mass Mnin the range from 6 to 11. Further may contain tailings quantities of vanadium, usually less than 15 parts per million.

The method of determining the bulk (Dmand srednecenovogo diameter (Dn) particles.

In accordance with the invention, the bulk (Dmand srednetsenovoj (Dn) the diameters of the particles, jedco Mesurments Ltd, UK).

The principle of measurement is to obtain from experiments particles using optical microscopy, the frequency table, which gives the number (ni) particles of each class (i) of diameters, each class is different intermediate diameter (diwithin this class. In accordance with French standard N-630 June 1981 Dmand Dnare given by the following formula.

CPEdnamesdiameternewDm=

CPEdacildiameterOICDn=

The relation of Dm/Dncharacterizes the size distribution of particles, sometimes called "the width of the size distribution of the particles. Measurements using analysis - jam Optomux is carried out using a microscope reverse action, allowing to observe the suspension of the carrier or catalyst particles with an increase from 16 to 200 times. The camera transmits images from the microscope to the computer that parses line by line and point by point on each line to determine the particle sizes or diameters for further classification.

P R I m e R 1. The preparation of a carrier.

A 30-liter reactor made of stainless stalno placed during the first stage in a nitrogen atmosphere at ambient temperature of 10.2 liters of the mixture, containing 10 mol dibutylamine in n-hexane, 6,45 l n-hexane and 1 l of vitaminology ether. In the second stage, where the speed of rotation peremestivsheesya system was maintained at 600 rpm, and the temperature of the reactor at 25aboutWith added 2.4 liters of tetraethyllead with constant speed within 12 hours After this reaction mixture was stood for 3 h at 25aboutC. the precipitate was washed 15 liters of n-hexane. The sediment washing was repeated 6 times. The obtained solid substance forms a carrier (n), on the basis of magnesium dichloride, containing 0.12 mol of vitaminology ether per mole of magnesium dichloride and less than 0.001 mol MgC communications. In the study under the microscope carrier (A) was in the form of spherical particles with a mass-average diameter of 21 μm and a very narrow distribution of particle size, defined by the relation Dm/Dnequal to 1.4.

The surface of the carrier (A) approximately 45 m2/g (bet). Structure of magnesium chloride in the media rather amorphous.

P R I m m e R 2. The preparation of the catalyst.

The suspension media (A) obtained in example 1 and containing 0.1 mole of magnesium dichloride in 150 ml of n-hexane were placed at ambient temperature in nitrogen in a 1-liter glass reactor system p the Wali at room temperature (25aboutC), was added 100 ml of a solution containing 0.2 mol/l chloride diethylamine in n-hexane. The mixture was stirred 1 h at 35aboutC. After stirring the suspension was heated to 50aboutWith and added for 4 h in 100 ml of a solution containing 0.16 mol/l of trichloride vanadyl and 0.04 mol/l tri-n-propoxide vanadium in n-hexane. Thus was obtained a new suspension, which was stirred 2 h at a temperature of 80aboutWith, then the stirring was stopped and allowed the catalyst to settle. After removal of the surface of the liquid phase, the catalyst was subjected to 2 consecutive washings, every time I use 200 ml of n-hexane at 50aboutWith another 3 successive washings using 200 ml of n-hexane at 25aboutWith each time.

Highlighted the catalyst (C) and kept under nitrogen atmosphere.

It contained, per mole of magnesium: 0.18 mol total vanadium (Vt), 0.09 mol of trivalent vanadium (V3+), 2.56 mol of chlorine (Cl) 0.04 mole vitaminology ether (DIAE), 0.1 mol n-propoxy group (OR), 0.1 mol of aluminum (Al).

Substances catalyst correspond as shown in table molar ratio V3+/Vt= 0,5, Vt/Mg= 0,18, Cl/Mg=2,56, Al/Mg=0,1, DIAE/Mg=0,04, OR/Mg=0.1 and 6.6% of vanadium in the catalyst.

The catalyst In the diameter Dm-21 μm and the particle size distributions of the Dm/Dn=1,4.

P R I m e R 3. The preparation of the catalyst.

Is carried out as in example 2, except that used 150 ml instead of 100 ml of a solution containing 0.2 mol/l chloride diethylamine in n-hexane and 100 ml of a solution containing 0.24 mol/l instead of 0.16 mol/l of trichloride vanadyl and 0.06 mol/l instead of 0.04 mol/l tri-n-propoxide vanadyl in n-hexane. Got the catalyst (C), the characteristics of which are given in the table.

P R I m e R 4. The preparation of the catalyst.

Is carried out as in example 2, except that the used solution containing 0.12 mol/l instead of 0.16 mol/l of trichloride vanadyl and 0.08 mol/l instead of 0.04 mol/l tri-n-propoxide vanadyl in n-hexane. Was the catalyst (D), the characteristics of which are given in the table.

P R I m e R 5. The preparation of the catalyst.

Is carried out as in example 2, except that after adding a solution of chloride diethylamine in n-hexane to a suspension of magnesium chloride and the mixture was stirred 2 h at 45aboutWith instead of 1 h at 35aboutWith and used a solution containing 0.18 mol/l instead of 0.16 mol/l of trichloride vanadyl and 0.02 mol/l vmsa in the table.

P R I m e R 6. The preparation of the catalyst.

Is carried out as in example 2, except that use 100 ml of a solution containing 0.16 mol/l of vanadium tetrachloride instead of 0.16 mol/ trichloride vanadyl and 0.04 mol/l Tetra-n-propoxide vanadium instead of 0.04 mol/l tri-n-propoxide vanadyl. Was the catalyst (F), the characteristics of which are given in the table.

P R I m e R 7 (comparative). The preparation of the catalyst.

Is carried out as in example 2, except that the used solution containing 0.3 mol/l instead of to 0.016 mol/l of trichloride vanadyl in n-hexane, the solution is completely absent tri-n-propoxide vanadium. Was the catalyst (G) whose characteristics are given in the table.

P R I m e R 8 (comparative). As example 2, except that applies chloride solution diethylaluminum. Was the catalyst (H), the characteristics of which are given in the table.

The molar ratio of X/OR the vanadium compounds used for the preparation of the catalyst in examples 2-6 is:

Example 2: 0,16 mol VOCl3+0,04 mol VO(OR)3: X/OR=0,16/0,04=4.

Example 3: 0,24 mol VOCl3+0.06 mol VO(OR)3:X/OR=0,24/0,06=4.<2 mol VO(OR)3:X/OR=0,18/0,02=9.

Example 6: 0,16 mol VCl4+0,04 mol V(OR)4:X/OR=0,16/0,04=4.

In comparative example 7 illustrates the use only of chloride without vanadium vanadium alkoxide.

The molar amount of the reducing agent, interact, per mol MgCl2in examples 2-6 the following:

Example 2: 20 mmol DEAC 100 mol MgCl2:0,2 mol DEAC/mol MgCl2.

Example 3: 30 mmol DEAC 100 mmol MgCl2:0,3 mol DEAC/mol MgCl2.

Example 4: identical to example 2, 0.2 mol DEAC/mol MgCl2.

Example 5: identical to example 2, 0.2 mol DEAC/mol MgCl2.

Example 6: identical to example 2, 0.2 mol DEAC/mol MgCl2< / BR>
(DEAC:diethylaluminium).

Comparative example 8 shows a method of obtaining a catalyst without using a reducing agent.

The molar amount of compounds V per mol MgCl2in examples 2-6 the following:

Example 2: 16 mmol VOCl3+4 mmol VO(OR)3100 mmol gCl2:0,2 mol V/mol MgCl2.

Example 3: 24 mmol VOCl3+6 mmol VO(OR)3100 mmol MgCl2:0,3 mol V/mol MgCl2.

Example 4: 12 mmol VOCl3+8 mmol VO(OR)3 the 100 mmol MgCl2:0,2 mol V/mol MgCl2.

Example 6: 16 mmol VCl4+4 mmol V(OR)4100 mol MgCl2: 0,2 mol V/mol MgCl2.

P R I m e R 9. Preparation of pre-polymer of ethylene.

A 5-liter stainless steel reactor equipped with an agitation system, rotating with a speed of 750 rpm, put 2 liters of n-hexane heated to 60aboutWith 8 mmol of triethylaluminum, 4 mmol of chloride diethylamine, and the catalyst (B) obtained in example 2 in an amount corresponding to 4 mmol of vanadium nitrogen atmosphere. Then the reactor was placed 1 liter of hydrogen under normal conditions, after that put the ethylene at 80 g/h for 4 h, after which the suspension is pre-polymer was cooled to ambient temperature and boiled away the n-hexane. Collected approximately 320 grams of powder pre-polymer, which was kept in a nitrogen atmosphere and which had the following characteristics:

spherical particles with an average diameter of mass 95 microns;

bulk density of 0.43 g/cm3;

the number of pre-polymer millimoles of vanadium 80,

Polymerization of ethylene in the gas sphere.

2.6-liter stainless steel reactor, nabendynamo from the previous reaction, inert and anhydrous, and the number of pre-polymer obtained previously, corresponds to 0.1 mmol of vanadium; the reactor was downloaded 1 mmol of triisobutylaluminum and the amount of hydrogen corresponding to a partial pressure of 0.05 MPa. The reactor was heated to 80aboutWith and served ethylene until then, until it reached a total pressure of 0.6 MPa, which is maintained continuously during the polymerization by adding ethylene. After 3 hours the reaction was received 600 g of polyethylene in powder form that has the following characteristics:

the vanadium content of 12 parts per million;

index melting point, measured at 190aboutWith a 5 kg load; 2.5 g/10 min;

bulk density of 0.42 g/cm3;

spherical particles with a diameter of 290 μm;

the distribution of molecular mass Mw/Mn=8.

P R I m e R 10. Polymerization of ethylene in suspension in n-hexane.

A 5-liter stainless steel reactor equipped with a stirrer rotating at a speed of 750 rpm, was added in nitrogen atmosphere with 2 l of n-hexane heated to 70aboutC, and 5 mmol of tri-n-oxyamine followed by the addition of catalyst (C), obtained in example 3 in an amount corresponding to 0.5 mmol of vanadium, and ashpole a suspension polymer was cooled to ambient temperature and boiled away the n-hexane, gathered about 480 g of polyethylene powder with the following characteristics:

spherical particles with a diameter of 280 microns;

bulk density 0,410 g/cm3;

mass content of fine particles having a diameter of less than 80 μm 0,5%

the stress index, measured at 190aboutWith a 5 kg load of 0.94 g/10 min;

the distribution of molecular mass Mw/Mn=9.

P R I m e R 11. Preparation of pre-polymer of ethylene and propylene.

A 5-liter stainless steel reactor with stirring, rotating with a speed of 750 rpm, sequentially in a nitrogen atmosphere and at ambient temperature (20aboutC) added 2 liters of n-hexane, 12 mmol of triisobutylaluminum, 40 mmol of chloroform and the catalyst (D) obtained in example 4 in an amount corresponding to 4 mmol of vanadium. The reactor was heated to 35aboutWith added to it a mixture containing 95 mol. ethylene and 5 mol. propylene with equal speed 80 g/h for 4 h After which the suspension is pre-polymer was cooled to ambient temperature, boiled away the n-hexane and collected 320 g of pre-polymer, which was kept in a nitrogen atmosphere and which had the following characteristics:

spherical particles with Elena 22%

the number of pre-polymer millimoles of vanadium 80,

Copolymerisation in the gas phase propylene and 1-butylene.

2.6-liter stainless steel reactor with agitation system for dry powder, rotating at a speed of 250 rpm, was placed in a nitrogen atmosphere to 150 g obtained in the previous reaction of a powder of a copolymer of propylene and 1-butylene, inert and anhydrous, and the number of pre-polymer obtained previously, corresponds to 0.1 mmol of vanadium; the reactor was downloaded 1.5 mmol of triisobutylaluminum, 3 mmol of chloroform and the amount of hydrogen corresponding to a partial pressure of 0.03 MPa. The reactor was heated to 50aboutWith and added a mixture containing 70 mol. propylene and 30 mole. 1-butylene, until the total pressure was 0.25 MPa, which is maintained throughout the copolymerization by adding a gas mixture. After 5 hours the reaction was obtained 490 g of a copolymer in the form of a friction-free powder with the following characteristics:

the vanadium content of 14 parts per million;

the melt index of 1.1 g/10 min;

mass content derived from 1-butene 28%

spherical particles with a diameter of 250 microns;

the distribution of molecular mass Mw/Mn

The copolymerization of ethylene and propylene in the gas phase.

2.6-liter stainless steel reactor with agitation system for dry powder, rotating at a speed of 250 rpm, was added under nitrogen atmosphere to 150 g of a powder of a copolymer of ethylene and propylene from a previous reaction, 4 mmol of triisobutylaluminum and 12.5 mmol of chloroform, followed by adding the previously obtained copolymer in an amount corresponding to 0.1 mmol of vanadium, and the amount of hydrogen corresponding to a partial pressure of a 0.012 MPa. The reactor was heated to 40aboutWith and added a gas mixture containing 70 mol. ethylene and 30 mol. propylene, until the total pressure was 0.4 MPa, which is maintained throughout the copolymerization by adding this gas mixture. After 5 hours the reaction was received 600 g of the copolymer in powder form, which had the following characteristics:

the vanadium content of 11 ppm;

the melt index of 0.8 g/10 min;

the mass content of the derived ethylene 63%

spherical particles with a diameter of 250 microns;

the distribution of molecular mass Mw/Mn=8,1;

the 470,000 on.

P R I m e p 13. Preparation of pre-polymer of ethylene and propylene.

Is carried out as in example 11, except that the used catalyst (F) of example 6 instead of the catalyst (D) of example 4.

Copolymerisation in the gas phase ethylene, propylene, ethylidenenorbornene.

2.5-liter stainless steel reactor with agitation system for dry powder, rotating at 250 Rev/min, in nitrogen atmosphere was added 150 g of a powder of a copolymer of ethylene, propylene, ethylidenenorbornene obtained from the previous reaction, 4 mmol of triisobutylaluminum, 12.5 mmol chloroform and the amount of hydrogen corresponding to a partial pressure 0,009 MPa, and then adding the previously obtained pre-polymer in an amount corresponding to 0.1 mmol of vanadium. The reactor was heated to 45aboutC. was Added a mixture of gases containing 75% ethylene and 25% propylene to a pressure of 0.5 MPa, which is maintained throughout the copolymerization by adding a gas mixture together with ethylidenenorbornene every 75 minutes after 5 hours the reaction was received 600 g of the copolymer in the form of a powder with the following characteristics:

the vanadium content of 12 parts per million;

induction less than 11% of

mass content of derivatives of ethylene 65%

mass content of derivatives of ethylidenenorbornene 3,3%

spherical particles with a diameter of 220 μm;

the distribution of molecular mass Mw/Mn=8

P R I m e R 14. Getting pre-polymer of ethylene and propylene.

Is carried out as in example 11, except that the used catalyst (G) of comparative example 7 instead of the catalyst (D) of example 4.

The copolymerization of ethylene and propylene in the gas phase.

Is carried out as in example 12, except that you use a pre-polymer obtained earlier instead of pre-polymer of example 12.

Under these conditions, the obtained copolymer had the following characteristics:

the vanadium content of 16 parts per million;

the melt index of 0.4 g/10 min MI5/190;

the diameter of 240 microns;

the distribution of molecular mass of 14.5 (Mw/Mn).

P R I m e R 15. Getting pre-polymer of ethylene and propylene.

Is carried out as in example 1 except that the used catalyst (H) of comparative example 8 instead of the catalyst (D) of example 4.

Hundredth, that used previously obtained pre-polymer instead of the pre-polymer of example 12. Under these conditions, was obtained copolymer with the following characteristics:

the vanadium content of 30 parts per million;

the melt index of 0.45 g/10 min;

mass content of derivatives of ethylene 72%

the diameter of 180 microns;

the distribution of molecular mass Mw/Mn=9.

P R I m e R 16. Getting pre-polymer of ethylene and propylene.

As example 11, except that the used catalyst (C) of example 3 instead of the catalyst (D) of example 4 and 8 mmol instead of 40 mmol of chloroform.

Copolymerisation in the gas phase ethylene and propylene.

Is carried out as in example 12, except that you use the previously obtained pre-polymer instead of pre-polymer from example 12 and a gas mixture containing 60 mol. instead of 70% ethylene and 40 mole. instead of 30% propylene. Under these conditions, was obtained copolymer in the amount of 600 g with the following characteristics:

the vanadium content of 11 ppm;

index melting 0.95 g/10 min;

mass content of derivatives of ethylene 52%

speechesceremonial weight 244,000.

P R I m e R 17. For the preparation of pre-activated media operate analogously to example 1, except that instead of dibutylamine use butylaniline and dietarily ether used in quantities of 0.5 l stirring is carried out with an intensity of 700 rpm (instead of 600 rpm), the temperature in the reactor 50aboutWith (instead of the 25aboutC), and tert-butyl chloride is added to the mixture of 6 hours (instead of 12 hours).

Thus obtained pre-activated media (K) is in the form of spherical particles with an average diameter mass (Dm) 15 μm and the ratio of Dm/Dn1,8. It contains 5 mol. disainlogo ether per mole of magnesium.

The preparation of the catalyst is identical to example 2, and instead of the carrier (A) use the media (To).

The resulting catalyst contains about 5.6 wt. vanadium is in the form of spherical particles with Dm=15 μm and the ratio of Dm/Dn=1,9.

P R I m e R 18. Preparation of pre activated carrier identical to the one described in example 1, with the use of 1.35 l of vitaminology ether (instead of 1 l), stirring is carried out at 120 rpm (instead of 600 rpm), tert-butyl chloride is added to the mixture of 20 hours (instead of 12 hours).

Polym diameter mass (Dm) 60 μm and the ratio of Dm/Dn=1,3. It contains 16 mol. vitaminology ether per mole of magnesium. The preparation of the catalyst is identical to example 2, and instead of the carrier (A) use a carrier (L). The resulting catalyst contains 8.8 wt. vanadium is in the form of spherical particles with Dm=60 μm and the ratio of Dm/Dn= 1,4.

1. The METHOD of producing CATALYST type Ziegler-Natta based on the precipitation of vanadium compounds in the liquid hydrocarbon reaction recovery of vanadium on solid media dichloride, magnesium, having a spherical particle with a mass-average diameter Dmfrom 10 to 100 microns and a narrow particle size distributions corresponding to the Dmto srednecenovom diameter number Dn1,3 1,8, and containing an electron donor, in particular dietarily ether, characterized in that, to improve catalyst with a high content of vanadium, the deposition is performed by the interaction in the liquid hydrocarbon reducing agent diethylformamide with soluble carbon compound of vanadium containing at least one halogen and one alkoxygroup, and solid media containing 84,0 - 95,0 mol. the magnesium dichloride, virtually swisa fact, what connection vanadium contains at least one group of halogen X and alkoxygroup OR in the molar ratio X/OR in the range from 1.5 to 9.

3. The method according to p. 1, characterized in that the vanadium compounds used trichloride of vanadium tri-n-propoxide vanadyl.

4. The method according to p. 1, characterized in that the interaction is carried out at a molar ratio diethylformamide to magnesium dichloride 0,2 0,3 1.

5. The method according to p. 1, characterized in that the interaction is carried out at a molar ratio of vanadium compounds to the magnesium dichloride 0,2 0,3 1.

6. The method according to p. 1, characterized in that the interaction is carried out at 35 80oC for 3 to 8 hours

 

Same patents:

The invention relates to the field of preparation of catalysts for hydrogenation of vegetable oils and fats

The invention relates to methods of producing catalysts for purification of exhaust gases of internal combustion engines

FIELD: chemistry.

SUBSTANCE: invention relates to field of catalyst. Described is method of obtaining catalyst for ethylene polymerization and copolimerisation of ethylene with alpha-olefins, containing vanadium compound on magnesium-containing carrier, which is obtained by interaction of solution of magnesium-organic compound with composition Mg(C6H5)2nMgCl2mR2O, where; n=0.37-0.7, m=2, R2O is ether with R=i-Am, n-Bu with chlorinating agent phenyltrichloromethane PhCCl3 with mole ratio PhCCl3/MgR2≥1.0, with further processing of carrier with alkylaluminium chloride and application of vanadium compound, with alkylaromatic ether being preliminarily introduced into magnesium organic compound at temperature 20-40°C with molar ratio alkylaromatic ether/Mg=0.05-0.2.

EFFECT: obtained catalyst makes it possible to obtain polymers with wide molecular-weight distribution, increased bulk density and high output.

1 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing pentacyclo[7.5.0.02.8.05.14.07.11]tetradeca-3,12-diene of formula The method is characterised by catalytic dimerisation of 1,3,5-cycloheptatriene (CHT). The catalyst system used is NbCl5-Et2AlCl. The reaction is carried out with molar ratio CHT:NbCl5:Et2AlCl=10:(0.1-0.3):4, in argon atmosphere, at 20-100°C, in benzene for 8-48 hours.

EFFECT: method enables to separately obtain the end product.

1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: method involves oil shale mixing in an organic solvent. At least 9 parts of an organic solvent are taken per one part of shale oil, the resulting mixture is oxidized by a catalytic oxidizing composition comprising hydrogen peroxide at a concentration of at least 50%, a salt selected from sodium molybdate, sodium tungstate, vanadyl sulfate, and an acid for oxidation reaction at the following ratio in molar proportions: salt selected from sodium molybdate, sodium tungstate, vanadyl sulfate:sulfur in oil = 1:500 to 1:50, hydrogen peroxide:sulfur in oil = 2:1 to 6:1, acid:sulfur in oil = 1:5 to 5:1. At that, 10 to 500 parts of the obtained mixture are taken per one part of the catalytic oxidizing composition, and the resulting mixture is treated at constant sonication power of 300 W for 2-6 hours, after which the solvent is removed and thermal cracking of the obtained mixture is carried out at 300-350°C for 3 to 6 hours.

EFFECT: objects allow to achieve a higher degree of sulfur removal.

12 cl, 3 ex

FIELD: chemistry.

SUBSTANCE: invention relates to the method of producing 2,3-dimethoxy-5-methyl-1,4-benzoquinone, a key intermediate in the synthesis of ubiquinones (coenzymes of the Qn series), in particular of coenzyme Q10, widely used in medical practice and cosmetology, as well as its synthetic analogue - idebenone - a drug for the treatment of Alzheimer's disease. The method consists in oxidizing 3,4,5-trimethoxytoluene with hydrogen peroxide in an organic solvent medium. Herewith the acid tetrabutylammonium salts of the vanadium-containing polyoxo-tungstate (C4H9)4N)5-nHn[γ-PV2W10O40], where the number of protons n in the cationic part of the polyox-tungstate varies from 1 to 2, as co-catalyst, HClO4 with respect to the catalyst, 0.5-1 equivalents, as the organic solvent, preferably acetonitrile is used, the process is carried out at the temperature of, at least, 30°C, at the molar ratio of 3,4,5-trimethoxytoluene: the catalyst is not lower than 40 and the concentration of 3,4,5-trimethoxytoluene is not higher than 0.4M, an aqueous solution of hydrogen peroxide with a peroxide content of, at least, 30 wt %, the process is carried out at the molar ratio of hydrogen peroxide: 3,4,5-trimethoxyphenol not less than 2.

EFFECT: desired product in high yield without the formation of a large amount of by-products.

2 cl, 1 tbl, 23 ex

FIELD: heterogeneous catalysts.

SUBSTANCE: catalyst contains porous carrier, buffer layer, interphase layer, and catalytically active layer on the surface wherein carrier has average pore size from 1 to 1000 μm and is selected from foam, felt, and combination thereof. Buffer layer is located between carrier and interphase layer and the latter between catalytically active layer and buffer layer. Catalyst preparation process comprises precipitation of buffer layer from vapor phase onto porous carrier and precipitation of interphase layer onto buffer layer. Catalytic processes involving the catalyst and relevant apparatus are also described.

EFFECT: improved heat expansion coefficients, resistance to temperature variation, and reduced side reactions such as coking.

55 cl, 4 dwg

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: palladium-containing hydrogenation catalyst, which can be used to control rate of autocatalytic hydrogenation reactions, is prepared by hydrogen-mediated reduction of bivalent palladium from starting compound into zero-valence palladium and precipitation of reduced zero-valence palladium on carbon material, wherein said starting material is tetraaqua-palladium(II) perchlorate and said carbon material is nano-cluster carbon black. Reduction of palladium from starting compound and precipitation of zero-valence palladium on carbon material are accomplished by separate portions.

EFFECT: increased catalytic activity, enabled catalyst preparation under milder conditions, and reduced preparation cost.

1 dwg, 1 tbl, 12 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: invention relates to environmentally friendly processes for production of isoalkanes via gas-phase skeletal isomerization of linear alkanes in presence of catalyst. Invention provides catalyst for production of hexane isomers through skeletal isomerization of n-hexane, which catalyst contains sulfurized zirconium-aluminum dioxide supplemented by platinum and has concentration of Lewis acid sites on its surface 220-250 μmole/g. Catalyst is prepared by precipitation of combined zirconium-aluminum hydroxide from zirconium and aluminum nitrates followed by deposition of sulfate and calcination in air flow before further treatment with platinum salts. Hexane isomer production process in presence of above-defined cat is also described.

EFFECT: increased catalyst activity.

5 cl, 2 tbl, 6 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention relates to methods for preparing carbon monoxide-conversion catalysts used in production of hydrogen, nitrogen-hydrogen mixture, and other hydrogen-containing gases. According to first option, active catalyst component, i.e. iron compound, is precipitated from solution with precipitation reagent, whereupon precipitate is separated from mother liquor and washed to form catalyst mass, which is molded and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. According to second option, iron compound is first mixed with promoting additives and cations of promoting additives are precipitated jointly with iron cations, resulting precipitate is separated from mother liquor, washed and subjected to heat treatment, re-washed, mixed with chromic anhydride and subjected to final heat treatment: at 280-420°C after molding or at 50-200°C before molding of catalyst mass. As iron compound in the first and second options, ferrous and ferric sulfates and, as precipitation reagent, carbonate salts or corresponding hydroxides are utilized. Promoting additives are selected from Cu, Mn, and Al or, in the second option, their mixture.

EFFECT: reduced content of sulfur in finished catalyst at the same catalyst activity.

3 cl, 1 tbl, 12 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention, in particular, relates to catalyst based on synthetic mesoporous crystalline materials and provides hydrocarbon conversion catalyst composed of: group VIII metal/SO42-/ZrO2-EOx, where E represents element of the group III or IV of Mendeleev's periodic table, x = 1.5 or 2, content of SO42- is 0.1 to 10% by weight, ZrO2/EOx molar ratio is 1:(0.1-1.0), which has porous crystalline structure with specific surface 300-800 m2/g and summary pore volume 0.3-0.8 cm3/g. Preparation method comprises precipitation of zirconium compounds, in particular zirconium hydroxide or zirconyl, under hydrothermal conditions in presence of surfactant to form mesoporous phase, which is stabilized with stabilizing agents: group III and IV elements. When stabilization is achieved, if necessary, acidity is adjusted and group VIII metal is added.

EFFECT: increased specific surface area and heat resistance at simplified technology.

9 cl, 2 dwg, 2 tbl, 6 ex

FIELD: chemical industry; methods of production of zirconium oxides

SUBSTANCE: the invention is pertaining to the field of chemical industry, in particular, to the methods of obtaining of zirconium oxide for production of the catalytic agents used, for example, in the reactions of the organic synthesis. The invention presents the method of obtaining of zirconium oxide for production of the catalytic agents, which includes the operations of dissolution of the zirconium salt in water, treatment of the solution with the alkaline reactant, settling of the metals hydroxides, filtration, separation of the mother-liquor from the settlings, the settlings water flushing, its drying, calcination and granulation and-or granulation by molding. At that dissolution of the source zirconium chloride and-or zirconium oxychloride is conducted in the sodium chloride solution with concentration of 200-250 g/dc3 till reaching of the concentration of zirconium of 20-120 g/dc3. Settling of zirconium oxyhydrate is conducted by the adding the initial chloride solution in the solution of the sodium hydroxide with concentration of 20-80 g/dm3 up to reaching the suspension pH equilibrium value - 5-8. Then the suspension is filtered up to the zirconium oxyhydrate pasta residual humidity of 40-80 %. The mother chloride solution is separated from the settlings of zirconium oxyhydrate and again use it for dissolution of the next batch of zirconium chloride and-or zirconium oxychloride. The settlings of zirconium oxyhydrate are subjected to drying at 80-100°C within 2-6 hours, then the dry settlings are suspended in the water at the ratio of liquid to solid L:S = (5-10 :1, the suspension is filtered, the sediment on the filter is flushed by water, the chlorides are wash off up to the residual concentration of ions of chlorine in the flush waters of 0.1-0.5 g/dm3, divided into 2 parts, one of which in amount of 60-80 % is subjected to drying and calcinations at the temperatures of 300-600°C, and other part in amount of 20-40 % is mixed with the calcined part of the settlings and subjected to granulation by extrusion at simultaneous heating and dehydration of the damp mixture of zirconium oxide and zirconium oxyhydrate with production of the target product. The technical result of the invention is improvement of quality of the produced zirconium oxide for production of the catalytic agents due to provision of the opportunity to use ZrO2 for the subsequent production of the various catalytic agents of the wide range of application and thereby improving the consumer properties of the produced production.

EFFECT: the invention ensures improvement of the quality of the produced zirconium oxide for production of the catalytic agents with improved consumer properties.

1 ex

FIELD: catalyst preparation methods.

SUBSTANCE: invention provides Fischer-Tropsch catalyst, which consists essentially of cobalt oxide deposited on inert carrier essentially composed of alumina, said cobalt oxide being consisted essentially of crystals with average particle size between 20 and 80 Å. Catalyst preparation procedure comprises following stages: (i) preparing alumina-supported intermediate compound having general formula I: [Co2+1-xAl+3x(OH)2]x+[An-x/n]·mH2O (I), wherein x ranges from 0.2 to 0.4, preferably from 0.25 to 0.35; A represents anion; x/n number of anions required to neutralize positive charge; and m ranges from 0 to 6 and preferably is equal to 4; (ii) calcining intermediate compound I to form crystalline cobalt oxide. Invention also described a Fischer-Tropsch process for production of paraffin hydrocarbons in presence of above-defined catalyst.

EFFECT: optimized catalyst composition.

16 cl, 12 tbl, 2 ex

FIELD: chemical industry; materials and the methods for the catalyst carrier manufacture.

SUBSTANCE: the invention is pertaining to the new mixed oxides produced from ceric oxide and zirconium oxide, which can used as the catalyzers or the catalyzers carriers for purification of the combustion engine exhaust gases. The mixed oxide possesses the polyphase cubical form of the crystallization and oxygenous capacity of at least 260/ micromoles of O2 /g of the sample and the speed of the oxygen extraction of more than 1.0 mg-O2/m2-minute, which are measured after combustion within 4 hours at the temperature of 1000°C. The invention also presents the substrate with the cover containing the indicated mixed oxide. The method of production of the polycrystallic particles of the indicated mixed ceric-zirconium oxide includes the following stages: i) production of the solution of the mixed salt which are containing, at least, one salt of cerium and, at least, one salt of zirconium in the concentration, sufficient for formation of the polycrystallic particles of the corresponding dry product on the basis of the mixed oxide. At that the indicated particles have the cerium-oxide component and zirconium-oxide component, in which these components are distributed inside the subcrystalline structure of the particles in such a manner, that each crystallite in the particle consists of a set of the adjacent one to another domains, in which the atomic ratios of Ce:Zr which are inherited by the adjacent to each other domains, are characterized by the degree of the non-uniformity with respect to each other and determined by means of the method of the X-ray dissipation the small angles and expressed by the normalized intensity of the dissipation I(Q) within the limits from approximately 47 up to approximately 119 at vector of dissipation Q, equal to 0.10 A-1; ii) treatment of the solution of the mixed salt produced in compliance with the stage (i),with the help of the base with formation of sediment; iii) treatment of the sediment produced in compliance with the stage (ii),using the oxidative agent in amount, sufficient for oxidizing Ce+3 up to Ce+4; iv) washing and drying of the residue produced in compliance with the stage (iii); and v) calcination of the dry sediment produced in compliance with the stage (iv),as the result there are produced polycrystallic particles of the oxide of ceric and zirconium in the form of the mixed oxide with the above indicated characteristics. The technical result is the produced mixed oxide possesses both the high oxygenous capacitance, and the heightened speed of the oxygen return in the conditions of the high temperatures.

EFFECT: the invention ensures production of the mixed oxide manufactured from ceric oxide and zirconium oxide and possessing the high oxygenous capacitance and the heightened speed of the oxygen return in the conditions of the high temperatures.

68 cl, 21 ex, 2 dwg

FIELD: production of catalytic compositions.

SUBSTANCE: proposed method includes combining and bringing into interaction at least one component of non-precious metal of group VII and at least two components of metal of VIB group in presence of proton liquid; then composition thus obtained is separated and is dried; total amount of components of metals of group VIII and group VIB in terms of oxides is at least 50 mass-% of catalytic composition in dry mass. Molar ratio of metals of group VIB to non-precious metals of group VIII ranges from 10:1 to 1:10. Organic oxygen-containing additive is introduced before, during or after combining and bringing components into interaction; this additive contains at least one atom of carbon, one atom of hydrogen and one atom of oxygen in such amount that ratio of total amount of introduced additive to total amount of components of metals of group VIII to group VIB should be no less than 0.01. This method includes also hydraulic treatment of hydrocarbon material in presence of said catalytic composition.

EFFECT: enhanced efficiency.

29 cl, 8 ex

FIELD: redox reaction catalysts.

SUBSTANCE: invention relates to methods for preparing vanadium-titanium oxide catalysts for redox reactions, e.g. for industrial processes of production of phthalic anhydride via oxidation of o-xylene, selective reduction nitrogen oxides, and detoxification of organochlorine compounds. Method of invention comprises following stages: providing titanyl sulfate solution; adding ammonia and then vanadium peroxide solution to titanyl sulfate solution or adding to the same vanadyl sulfate or oxalate and then ammonia solution; optionally ageing suspension resulting after mixing of solutions; filtration; and calcinations at 450°C.

EFFECT: increased heat resistance of active chlorobenzene oxidation catalyst and reduced catalyst preparation time (10-12 h instead 72 h as in a known method).

1 tbl, 3 ex

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