Method for production of linear olefins useful in linear alcohol manufacturing

FIELD: organic chemistry.

SUBSTANCE: claimed method includes a) reaction of carbon monoxide and hydrogen in presence of effective amount of Fischer-Tropsch catalyst; b) separation of at least one hydrocarbon cut containing 95 % of C15+-hydrocarbons from obtained hydrocarbon mixture; c) contacting separated cut with hydrogen in presence of effective amount of hydration catalyst under hydration conditions; d) treatment of hydrated hydrocarbon cut by medium thermal cracking; and e) separation of mixture, including linear C5+-olefins from obtained cracking-product. Method for production of linear alcohols by oxidative synthesis of abovementioned olefins also is disclosed.

EFFECT: improved method for production of linear olefins.

12 cl, 3 tbl, 1 dwg, 2 ex

 

The present invention relates to a process for the preparation of linear olefins and to a method for linear alcohols from registertimer source material that at least partially based on linear olefins.

There are various ways to obtain a linear olefins are known from the technical field. The present invention relates to the preparation of linear olefins in a way that also involves the reaction of hydrocarbon synthesis Fischer-Tropsch (Fischer-Tropsch).

This method is also disclosed in U.S. patent No. 4579986. This U.S. patent discloses a method of obtaining a linear C10-C20olefins, the method includes obtaining a mixture of hydrocarbons, essentially consisting of linear paraffins by:

(a) contacting a mixture of carbon monoxide and hydrogen at elevated temperature and pressure containing cobalt catalyst,

(b) separation from paraffin mixture obtained in this way, the heavy fraction, which essentially consists of From a20+paraffins, and

(C) conversion of at least this heavy fraction ("wax") by moderate thermal cracking in a mixture of hydrocarbons consisting essentially of linear olefins and containing the desired10-C20olefins.

Although the method of cracking of paraffins in accordance with U.S. patent No. 4579986 works successfully, nevertheless OST which is place for improvements. In particular, if the starting point is obtaining registertimer source material that can be used as (part of) the source material for the reaction of hydroformylation to obtain a linear alcohols, detergents and plasticizers, the method according to U.S. patent No. 4579986 can be improved. Namely, linear alcohols, plasticizers typically contain from 7 to 11 carbon atoms, while linear alcohols, detergents typically contain from 12 to 15 carbon atoms. Accordingly, the hydrocarbon fraction is obtained for use, at least partially as a source material for hydroformylation must contain a significant proportion With6-C14olefins, at least 80 wt.%, but preferably at least 85 wt.% one of them consists of the corresponding linear α-olefins. It was found that by hydrogenation paraffin feedstock before it is subjected to the treatment method of moderate thermal cracking, get With6-C10and C11-C14linear α-olefins of very high quality: received6-C14the olefins contained in a mixture With5+olefins) are more than 800 wt.% from C6-C14linear α-olefins.

Therefore, in the first aspect of the present invention regarding the seeking to the way to obtain a mixture, include5+linear olefins, the method includes the following stages:

(a) interaction of carbon monoxide and hydrogen in the presence of an effective amount of catalyst Fischer-Tropsch under the reaction conditions of the Fischer-Tropsch;

(b) separating from the resulting hydrocarbon mixture, at least one hydrocarbon fraction, 95 wt.% which consists of hydrocarbons containing 15 carbon atoms or more;

(C) contacting this hydrocarbon fraction with hydrogen in the presence of an effective amount of hydrogenation catalyst at hydrogenation conditions;

(d) processing the received gidrirovannoe hydrocarbon fraction by moderate thermal cracking and

(e) the Department obtained from the cracking product mixture comprising From5+linear olefins.

The mixture of product, including5+linear olefins, preferably is a mixture comprising From5-Cmlinear olefins, where m is an integer from 10 to 20, preferably 12 to 18, more preferably 12-15. A very useful mixture is a mixture comprising From5-C14linear olefins. This mixture comprises at least 20 wt.% and more preferably from 25 to 50 wt.%. With11-C14linear α-olefins. With5-C10linear α-olefins typically up to 75 wt.% stream site is preferably from 40 to 75 wt.%. The balance to 100 wt.%, constituting a relatively small portion of the stream consists of hydrocarbons other than those specified olefins, such as C4hydrocarbons, and associated With5+linear alkanes, isoalkanes, isoolefine, internal olefins and dienes. Typically, this small fraction of other hydrocarbons not exceeding 20 wt.% and is eligible is less than 10 wt.%.

At stage (a) of the method according to the present invention, the hydrocarbons are formed by the interaction of carbon monoxide and hydrogen in suitable conditions. Basically, the preparation of hydrocarbons from a mixture of carbon monoxide and hydrogen at elevated temperature and pressure in the presence of an effective quantity of a suitable catalyst known as a synthesis of hydrocarbons by the Fischer-Tropsch process. The catalysts used in the synthesis of hydrocarbons, usually referred to as catalysts for Fischer-Tropsch, and they usually include one or more metals of Groups 8, 9 and 10 of the Periodic Table of the Elements, optionally together with one or more promoters and material media. In particular, iron, Nickel, cobalt and ruthenium are well-known catalytically active metals for such synthesis. The catalyst for the Fischer-Tropsch process used in stage (a) of the method according to the present invention comprises a porous carrier, particularly a carrier-based refractory(difficult creceremos) oxide. Examples of suitable refractory oxide carriers include alumina, silica, titanium dioxide, zirconium dioxide or a mixture thereof, such as silica-alumina, or a physical mixture, such as silicon dioxide and titanium dioxide. Very suitable carriers are those that include titanium dioxide, zirconium dioxide or a mixture thereof. Media based on titanium dioxide are preferred, in particular titanium dioxide, obtained in the absence of sulfur-containing compounds. This carrier may optionally include up to about 50 wt.% another refractory oxide, typically silicon dioxide or aluminum oxide. More preferably the additional refractory oxide, if it is present, up to 20 wt.%, even more preferably up to 10 wt.% from the mass media.

Preferred catalytically active metal is cobalt, but can also be used Nickel, iron, and ruthenium. The number present in the catalyst is catalytically active metal varies widely. Typically, the catalyst comprises 1-100 mass parts of such metal on 100 mass parts of the carrier, preferably 3-60 mass parts, more preferably 5-40 mass parts. The above amount of catalytically active metal refers to the total quantity of metal in elemental the Orme and can be determined by known method of elemental analysis. For convenience, the cobalt will be referred to as "the catalytically active metal", but it must be emphasized that instead of cobalt, or in addition to it can also be used for other catalytically active metals, above.

In addition to the cobalt catalyst may include one or more promoters that are known to specialists in this field of technology. Suitable promoters include manganese, zirconium, titanium, ruthenium, platinum, vanadium, palladium and/or rhenium. The amount of promoter, if present, is typically from 0.1 to 150 mass parts, for example from 1 to 50 mass parts per 100 mass parts of the media.

The catalyst for the Fischer-Tropsch typically does not contain alkali or alkaline-earth metals, with the exception of a certain amount of impurities introduced starting material in the process of obtaining catalysts of the present invention. Typically the atomic ratio of alkali or alkaline-earth metals to the metallic cobalt is less than 0.01, preferably less than 0.005.

The conditions of the Fischer-Tropsch process used in stage (a) of the present invention, typically include a temperature in the range from 125 to 350aboutC, preferably from 150 to 275aboutC, and a pressure in the range from 5 to 150 bar(abs). Stage (a) of the method according to the present invention can perform the ri usually set pressure, for example up to 80 bar(abs), are eligible for up to 50 bar(abs), but you can also use higher pressure.

In a preferred embodiment of the present invention stage (a) includes the interaction of carbon monoxide with hydrogen at a temperature in the range from 125 to 350aboutC and a pressure in the range from 5 to 150 bar(abs), in the presence of a catalyst comprising cobalt on the media, including titanium dioxide. Suitably, the catalyst and the conditions of the method (a) are chosen so that we get at this stage the product is included from 2 to 20 wt.% hydrocarbon fraction With11-C14while this hydrocarbon fraction comprises from 10 to 60 wt.% calculated on the total weight of this fraction With11-C14mono-olefins. This is achieved, for example, using a catalyst Fischer-Tropsch cobalt-based and titanium dioxide at temperatures from 175 to 275aboutC and a working pressure of from 20 to 80 bar(abs).

The flow of hydrogen and carbon monoxide (synthesis gas) is typically carried out when the atomic ratio of from 0.5 to 4, especially from 1 to 3. In a preferred embodiment, the atomic ratio of hydrogen and carbon monoxide is in the range from 1.5 to 2.5.

Stage (a) step of the reaction of the Fischer-Tropsch process can be performed using different reactor types and modes of reaction, for example in the mode of the fixed layer, the mode su is pensionnoi phase or in the fluidized bed. It should be clear that the size of the catalyst particles may vary depending on the mode of reaction, which is the catalyst. An ordinary person skilled in the art can select the most suitable particle size for a given reaction mode.

In addition, it should be clear that the expert can select the most suitable conditions for a specific reactor configuration and the specific mode of action. For example, the preferred hourly space velocity of the gas is from 500 to 2500 Nl/l/h. When it is desirable that the process of synthesis of hydrocarbons are operated in the suspension phase, preferably hourly space velocity of the gas is chosen in the range from 1500 to 7500 Nl/l/h.

At the stage (b) of the method according to the present invention, at least one hydrocarbon fraction, which is 95 wt.%, preferably, at least 98 wt.% consists of hydrocarbons containing 15 carbon atoms or more (hereinafter fraction With15+), separated from a mixture of hydrocarbons, obtained at the previous stage (a) synthesis of hydrocarbons by the Fischer-Tropsch process. Separation can be accomplished by methods well known in the prior art. Preferably this separation includes distillation processing, namely fractional distillation. You can use the traditional distillation methods.

Stage section is of (b) may only be made by distillation, but it can also include a combination of fractional distillation with other separation processing, such as distillation light ends or condensation. For example, the hydrocarbon product from step (a) can first be divided into a liquid stream and a gaseous stream by passing the hydrocarbon product from step (a) through the condenser, suitably operated at the same temperature and pressure, as set on the stage (a). The liquid stream from the condenser can then be removed as15+ fraction, whereas in the gaseous stream of hydrocarbons the major amount of hydrocarbons contains less carbon atoms (typically to14). The gaseous stream is then oiaut and processed by the method of fractional distillation to extract the desired hydrocarbon fractions for further processing.

Fraction With15+ usually does not contain more than 5 wt.%, eligible more than 2 wt.% hydrocarbons containing more than n carbon atoms, where n is defined below. Fraction With15+which is used as the source material for the stage (s)can be a fraction With15+ as such, but may also represent a fraction With15-Cnwhere n denotes an integer having a value of at least 18, preferably at least 20 and not more than 40, preferably not bol is e 35, more preferably not more than 30. The upper limit is suitably chosen so that the source material for the stage paraffin cracking (d) was completely gaseous at cracking conditions to avoid coke formation in the cracking unit paraffins. The rest of the faction Withn+ you can also fully or partially, to use as source material for the stage (C) of the method according to the present invention or can be subjected to other processing, such as heavy paraffin cracking with the formation of petroleum products such as naphtha, kerosene and gasoil. The expression "fraction15+", as used hereinafter, includes fraction With15-Cndefined above.

At the stage (C) carry out the hydrogenation of the fraction15+. The hydrogenation is typically carried out in the presence of a hydrogenation catalyst and hydrogen at a temperature of from 100 to 400aboutC, preferably from 100 to 300aboutS, more preferably from 150 to 275aboutS, even more preferably from 180 to 250aboutC. Typically the partial pressure of hydrogen is in the range from 10 to 250 bar(abs), preferably from 10 to 150 bar(absolute), more preferably from 10 to 50 bar(abs), even more preferably from 15 to 45 bar(abs). The hydrogen can be fed to the stage hydrogenation with an hourly volume rate of gas in the range from 100 to 10000 Nl/l of the volume of the reaction is ionic zone/hour more preferably from 250 to 5000 Nl/l of the volume of reaction zone per hour. Processing fractions With15+ carry out typically the flow on stage hydrogenation when the volume-weighted velocity in the range from 0.1 to 5 kg/l volume of reaction zone per hour, more preferably from 0.25 to 2.5 kg/l volume of reaction zone per hour. The amount of hydrogen relative to the fraction15+ can be set from 100 to 5000 Nl/kg and preferably ranges from 250 to 3000 Nl/kg

The hydrogenation catalysts known to experts in the art and are commercially available, or can be obtained by methods well known in the art. Typically, the hydrogenation catalyst comprises as catalytically active component is one or more metals selected from groups 6, 8, 9 and 10 of the periodic Table of Elements, in particular one or more metals selected from molybdenum, tungsten, cobalt, Nickel, ruthenium, iridium, osmium, platinum and palladium. Preferably the catalyst, as the catalytically active component comprises one or more metals selected from Nickel, platinum and palladium. Particularly suitable catalyst as the catalytically active component comprises Nickel.

Catalysts for use in the processing phase, the hydrogenation typically include refractory metal oxide or silicate as the e media. Suitable materials carriers include silica, alumina, silica-alumina, zirconium dioxide, titanium dioxide or mixtures thereof. The preferred materials of media for inclusion in the catalyst used in the method according to the present invention are silica, alumina, silica-alumina and diatomaceous earth (kieselguhr).

The catalyst may include a catalytically active component in an amount of from 0.05 to 80 mass parts per element, preferably from 0.1 to 70 mass parts per 100 mass parts of the material medium. The amount of catalytically active metal present in the catalyst used depends on the specific metal. One particularly suitable catalyst designed for use on stage hydrogenation, includes Nickel in an amount ranging from 30 to 70 mass parts (per element) 100 mass parts of the material medium. The second is particularly suitable catalyst comprises platinum in an amount in the range of 0.05 to 2.0 mass parts per 100 mass parts of the material medium.

At the next stage (d) provide moderate thermal cracking gidrirovannoe hydrocarbon fraction obtained in stage (C). This mild thermal cracking may be carried out by methods known from the Urals branch of the ar technology. In a preferred variant embodiment of a mild thermal cracking stage (d) is carried out in the presence of water vapor. Such processing is described, for example, in the aforementioned U.S. patent No. 4579986, which is included in this description by reference. Suitable mild thermal cracking includes cracking gidrirovannoe hydrocarbon fraction at a temperature of from 450 to 675aboutC, preferably from 480 to 600aboutC, a pressure of from 1 to 50 bar(abs), preferably from 1 to 10 bar(abs) and more preferably from 1 to 5 bar(abs), and residence time in the reactor is from 0.5 to 20 seconds, preferably from 1 to 10 seconds. Thermal cracking can be carried out using a diluent or without him. Suitable diluents include water vapor and inert gases, of which water vapor is preferred. In case it is used the amount of water vapor up to 40 wt.% (based on the feed amount of hydrocarbons), preferably from 3 to 30 wt.%. As indicated, as a diluent can also be used an inert gas. Intended for such use inert gas is a gas which does not affect the cracking reaction, decomposing and/or reacting with the hydrocarbon reactants and splitting products. Examples of suitable inert gases include nitrogen and noble gases, so the e as helium and argon. It was found that the use of the diluent has a positive effect on the number of formed products.

In a preferred embodiment, mild thermal cracking involves the following stages:

(d1) Association of diluent and gidrirovannoe hydrocarbon fraction in the evaporator and

(d2) thermal cracking the evaporated hydrocarbon fraction.

The evaporator is typically operates at a temperature high enough to evaporate hydrogenated hydrocarbon stream. Usually it is at least 350aboutWith, suitably, at least 400aboutC, the maximum temperature does not exceed 600aboutWith, eligible 500aboutTo avoid excessive cracking. Stage of the cracking (d2) is typically carried out at a temperature from 450 to 650aboutWith, eligible 480-600aboutWith pressure at least 1 bar(abs), and usually not exceeding 300 bar(abs), suitably from 1 to 10 bar(abs), more suitably from 1 to 5 bar(abs), residence time in the reactor is from 0.5 to 20 seconds, suitably from 1 to 10 seconds, in the presence of a diluent.

As described below, the following stage (s) can provide a stream of heavy hydrocarbons Withm+that can, at least partially, to return by recycling on stage cracking (d), either directly or through a stage of hydrogenation (C). When this mode works the stage of thermal cracking (d) is suitably carried out in such conditions, the conversion of hydrocarbons in a single pass is in the range from 10 to 50 wt.%, preferably from 10 to 35 wt.% and more preferably from 15 to 30 wt.% calculated on the total weight of the hydrocarbons passing through the reactor for thermal cracking during this pass.

At the next stage (e) of the desired mixture containing5+ linear olefins are separated from the product of cracking. In principle, you can use any method of separation, suitable for separating a mixture of hydrocarbons With5+ from the product of cracking. Such methods may include a method of molecular distillation, such as separation using a film evaporator, the method of distillation of light fractions and fractional distillation at atmospheric or reduced pressure. For the purposes of the present invention, one particularly suitable method involves the following stages:

(E1) cooling the cracking of the product and separation from the cooled cracking-product liquid cracking product containing5+ hydrocarbons, and

(E2) separating liquid from the cracking product mixture comprising From5-Cmlinear olefins.

Typically, cooling and first stage separation (E1) is carried out in a separator for separating gas and liquid. Hot cracking product is first cooled to a temperature at which the desired5+ hydrocarbons become liquid, and gaseous n the FL 1-C4as well as any used for cracking the diluent can be removed in the form of gases. It should be clear that a small number With5+ hydrocarbons ends in a gaseous stream, while a small number With4- hydrocarbons ends in fluid flow. It should be clear that used the exact temperature depends on the pressure applied. The flow of fluid extracted from the separator separation of gas/liquid contains the desired5+ hydrocarbons, and it is served to the next stage separation (E2), where separate thread With5-Cmhydrocarbons containing mixture With5-Cmlinear olefins. This stage can suitably be implemented in organoclay section of the distillation column, optionally with the use of a Stripping gas such as water vapor, nitrogen, helium or argon. Stream5-Cmhydrocarbons containing mixture With5-Cmlinear olefins are then removed as the top faction. The next phase separation (E3)m+ bottom fraction eligible, at least partially, return by recycling on stage hydrogenation of (s) and/or stage of cracking (d).

The mixture containing the5+ linear olefins, obtained as described above, typically includes from 20 to 50 wt.% With11-C14linear α-olefins and from 40 to 75 m is S.% C 5-C10linear α-olefins and, therefore, represents a highly suitable source material for the production of linear alcohols, detergents and plasticizers in the reaction of hydroformylation.

Therefore, in its second aspect the present invention relates to a method for linear alcohols by reacting registertimer source material with carbon monoxide and hydrogen in the presence of an effective amount of catalyst hydroformylation in terms of hydroformylation where registergui source material, at least partially, consists of a mixture of C5+ linear olefins, obtained by the method described above. Very suitable for such purposes, the method is a method in which registergui source material obtained by fractionation:

(a) first stream of hydrocarbons obtained as the result of the interaction of carbon monoxide and hydrogen in the presence of an effective amount of catalyst Fischer-Tropsch process in the conditions of the reaction, Fischer-Tropsch, and

(b) second stream of hydrocarbons, consisting of a mixture comprising From5+ linear olefins, obtained by the above method.

The mass ratio of the first stream of hydrocarbons and a second stream of hydrocarbons may vary within wide limits, but is eligible is the range from 0.1:1 to 30:1, preferably from 1:1 to 30:1 and more preferably from 5:1 to 25:1.

Processing by fractionation of qualifying matches under division (b) of the method in accordance with the first aspect of the present invention described above.

The first stream of hydrocarbons is a reaction product of the synthesis of hydrocarbons by the Fischer-Tropsch process, all eligible4+ the product obtained by the reaction of a hydrocarbon synthesis Fischer-Tropsch process. This reaction, its conditions and ways of its implementation are described in detail above. The first stream of hydrocarbon contains from 2 to 20 wt.%, more suitably from 3 to 10 wt.% With11-C14of hydrocarbons. Of those With11-C14hydrocarbons 10-60 wt.%, suitably from 15 to 50 wt.% consists of a11-C14linear mono-olefins.

The second stream of hydrocarbons comprises at least 95 wt.%, preferably, at least 98 wt.% of hydrocarbons containing 5 or more carbon atoms, and typically contains from 20 to 50 wt.% With11-C14linear α-olefins, this can also be achieved levels of 30 wt.% and even 35 wt.%. Number5-C10linear α-olefins in the second stream of hydrocarbons typically ranges from 40 to 75 wt.%. The balance to 100 wt.% are hydrocarbons other than those specified olefins, such as C4hydrocarbons and associated With5 + linear alkanes, isoalkanes, isoolefine, internal olefins and diene.

The drawing shows a simplified diagram of a method in accordance with the second aspect of the present invention.

In this drawing thread 64+ hydrocarbons, which are the reaction product of a Fischer-Tropsch derived in the method for the synthesis of hydrocarbons by the Fischer-Tropsch (not shown), is passed into the fractionation column 1. Fraction 7 (C4-C5), fraction 8 (C6-C10), fraction 9 (C11-C14), fraction 10 (C15-C30) and fraction 11 (C30+) release. Fraction 8 (C6-C10) and fraction 9 (C11-C14pass in the installation of 5 hydroformylation, where their conversion into alcohols, plasticizers 17 and alcohols, detergents 18. Fraction 11 (C30+) you can skip to the cracking of paraffins (not shown) for conversion, such as middle distillates, such as naphtha and kerosene. Fraction 10 (C15-C30pass in the installation hydrogenation of 2 with obtaining gidrirovannoe fraction 12, which is then subjected to cracking in the installation 3 moderate thermal cracking. The cracking product 13 is directed in the installation fractionation 4, from which the extract fraction 15 (C4-), fraction 16 (C5-C14) and the fraction 14 (C15+). The last return by recycling to the cracking unit 3, whereas the fraction 16 5-C14) combined with a stream of 6 hydrocarbon product4+ the reaction of the Fischer-Tropsch and passed into the fractionation column 1.

Further, the invention is illustrated by the following examples, however the invention is not limited to these specific examples.

Example 1

Two commercially available hydrogenation product obtained in the reactor Fischer-Tropsch (available under the trademarks SX-30 SX-50), unite in a mass ratio SX-50 SX-30, equal to 70:30, and then add 5 wt.% (based on the total weight of SX-30 SX plus-50) hexadecane to play hydrogenated in the reaction of the Fischer-Tropsch16+ the source material for the installation of paraffin cracking. The composition of such a starting material shown in table 1.

Table 1
The composition of the source material
-FactionAfter hydrogenation (wt.%)
With14- paraffins0,0
With15-C20waxes32,9
With21-C25waxes26,4
With26-C30waxes35,3
With31+waxesof 5.4

For this cracking reaction using the Ali of the reaction tube AISI 310 (length 30 cm, a volume of 10 ml). Accordingly, gidrirovannoe fraction was then combined with the feed rate of 12 grams per hour with recycle fraction With15-C20isolated from the cracking product when the recirculation ratio (i.e. the mass ratio of recycle fraction to gidrirovannogo product) of 3.2. United paraffin stream is metered directed at 70aboutFrom heated storage tanks into the evaporator, where he was teamed with helium at a molar ratio of helium to the hydrocarbon equal to 1. The temperature in the evaporator was approximately 400aboutC. the Evaporated stream is then sent to the cracking zone where it was cracking at a temperature of 560aboutC and a pressure of 3 bar(abs) when the residence time in the cracking zone 4 sec. The cracking product is then separated into a gas fraction (helium and C1-C4hydrocarbons), the fraction of liquid cracking product5-C14and liquid product15-C20which is recycled to combine with vegegation material before it enters the evaporator. The composition of the cracking product1-C14shown in table 2.

Table 2
The composition of the cracking product
Factionwt.%1)Mono-olefinthe AU.% 1)
With1-C4(par.+olef.)37With11-C12the 9.7
With5-C14(par.+olef.)63With13-C149,2
1)calculated on the total mass of educated1-C14

Example 2

The liquid fraction of the cracking product5-C14obtained in Example 1 was subjected to fractionation using a distillation column with 15 plates, filled with Fischer reagent, with a coefficient of irrigation 25. Fraction With11/S12and the fraction With13/S14obtained by fractionation, were subjected to treatment with hydroformylating the corresponding alcohols. The composition of both fractions are shown in Table 3.

Hydroformylation both fractions was carried out by loading the autoclave with a capacity of 1.5 l 565 g of starting material, consisting of 53 wt.% from the fraction11/S12and fraction13/S14at 34 wt.% from isooctane (as diluent), 1 wt.% from n-decane or tetradecane as internal standard respectively, for the fraction11/S12and fraction13/S14) and 12 wt.% from 2-ethylhexanol, in which were dissolved KOHN and catalyst hydroformylation. Rolled the ATOR of hydroformylation was based on octanoate cobalt as a cobalt precursor and a 9-eicosyl-9-phosphabicyclononanes as a ligand, and these substances are added in an amount such that the amount of catalyst was 0.25 wt.% in calculating the total amount of added source material, and the molar ratio of ligand/cobalt was 1.2. The amount of KOH present in 2-ethylhexanol, was such that the molar ratio To/From amounted to 0.4. Then made hydroformylation at a temperature of 192aboutAnd pressure of the synthesis gas (molar ratio of N2/CO=2) 70 bar(abs). The reaction time was 3 hours. The conversion was >98.5 per cent.

The resulting crude alcohol product is then subjected to single-stage evaporative distillation (rotary evaporator operating at a pressure of 100 bar(abs), and the bath temperature of 80-220aboutC), saponification by adding NaHBH4when 50-90aboutWith a water rinse (twice) at 80-90aboutWith the removal of the formed inorganic salts and distillation treatment under reduced pressure to remove light and heavy products (removal of the "top and tail chasing").

The alcohol composition obtained products are shown in Table 3.

Table 3
Hydroformylating the cracking of product
-FactionThe cracking product11/12< / br>
(wt.%)
Sleep is t 12/13< / br>
(wt.%)
The cracking product13/14< / br>
(wt.%)
Alcohol With14/15< / br>
(wt.%)
C10
Alkenes (all)3,3
n-alkane<0,1
Linear alcohol<0,1
C11
1-alkene43,9
Other alkenes1)a 3.9
N-alkane0,2<0,1
Linear alcohol<0,1<0,1
C12
1-alkene40,51,0
Other alkenes1)4,60,3
N-alkane1,6<0,1<0,1<0,1
Linear alcohol41,3<0,1
Branched alcohol7,1
C13
1-alkene1,044,5
Other alkenes1)0,7the 4.7
N-alkane0,21,4<0,1
Linear alcohol34,40,8
Branched alcohol16,0
C14
1-alkeneof 40.3
Other alkenes1)4,5
N-alkane1,4 <0,1
Linear alcohol42,2
Branched alcohol0,913,3
C15
1-alkene0,7
Other alkenes1)0,5
N-alkane0,2<0,1
Linear alcohol30,4
Branched alcohol12,3
C16
Branched alcohol0,8
1)other alkenes include dieny, branched alkenes and internal alkenes

1. The method of obtaining a mixture containing a5+linear olefins, comprising the following stages:

(a) the interaction of the oxide with the carbon and hydrogen in the presence of an effective amount of catalyst Fischer-Tropsch under the reaction conditions of the Fischer-Tropsch process;

(b) separating from the resulting hydrocarbon mixture, at least one hydrocarbon fraction, 95 wt.% which are hydrocarbons containing 15 carbon atoms or more;

(c) contacting this hydrocarbon fraction with hydrogen in the presence of an effective amount of hydrogenation catalyst at hydrogenation conditions;

(d) processing the received gidrirovannoe hydrocarbon fractions by thermal cracking at a temperature of from 450 to 675°and

(e) the Department obtained from the cracking product mixture comprising From5+linear olefins.

2. The method according to claim 1, wherein a mixture comprising From5+linear olefins is a mixture comprising From5-Cmlinear olefins, where m denotes an integer from 10 to 20.

3. The method according to claim 1 or 2, in which phase thermal cracking (d) is carried out in the presence of a diluent.

4. The method according to claim 3, in which the diluent is water vapor.

5. The method according to claim 2, in which the separation stage (e) involves the following stages:

(E1) cooling the cracking of the product and separation from the cooled cracking-product liquid cracking product containing5+hydrocarbons, and

(E2) separating liquid from the cracking product mixture comprising C5-Cmlinear olefins.

6. The method according to claim 5, in which the separation stage (is) includes the additional step

(E3) recycling at least part of the heavy fraction Withm+with stage separation stage cracking (d) and/or stage hydrogenation (C).

7. The method according to claim 1, in which stage of thermal cracking (d) is carried out in such conditions that the conversion of hydrocarbons in a single pass is in the range from 10 to 50%, based on the total weight of hydrocarbons, is passed through the reactor for thermal cracking during this pass.

8. A method of obtaining a linear alcohols by reacting registertimer source material with carbon monoxide and hydrogen in the presence of an effective amount of catalyst hydroformylation in terms of hydroformylation where registergui source material at least partially consists of a mixture comprising From5+linear olefins, obtained by the method according to any one of claims 1 to 7.

9. The method according to claim 8, in which registergui source material was obtained, subjecting them to fractionation

(a) first stream of hydrocarbons obtained as the result of the interaction of carbon monoxide and hydrogen in the presence of an effective amount of catalyst Fischer-Tropsch process in the conditions of the reaction, Fischer-Tropsch, and

(b) second stream of hydrocarbons, consisting of a mixture comprising C5+linear olefins, obtained by the method according to any one of claims 1 to 7.

10. The method according to claim 9, in which the mass is the ratio of the first stream of hydrocarbons and a second stream of hydrocarbons is in the range from 0.1:1 to 30:1.

11. The method according to claim 9 or 10, in which the first stream of hydrocarbon contains from 2 to 20 wt.% With11-C14hydrocarbons, of which 10-60 wt.% consist of With a11-C14linear monoolefins.

12. The method according to claim 9, in which the second stream of hydrocarbons comprises from 20 to 50 wt.% With11-C14linear α-olefins.



 

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28 cl, 4 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: catalyst contains following active components: Pd (0.001-1%), Bi (0.001-5%), at least of Ag, Cu, Zn, K, Na, Mg, Ca, Be, Sn, Pb, Cd, Sr, Ba, Ra, Mn, Zr, Mo, and Ge (0.001-10%), and at least one of rare-earth metals deposited on porous inorganic carrier (the balance.). Catalyst is capable of selectively and rapidly hydrogenating strongly unsaturated hydrocarbons such as alkynes. Catalyst is suitable for industrial cracking process and is characterized by favorable long regeneration period, long service time, and low cost.

EFFECT: improved performance characteristics of catalyst at low cost.

23 cl, 5 tbl, 22 ex

FIELD: petroleum chemistry.

SUBSTANCE: claimed method includes oligomerization of one or more alpha-olefins with ethylene in presence of metal-containing catalytic system, using one or more bisaryl pyrimidine-MXa complex and/or one or more [bisaryl pyrimidine-MYpLb+]q- complex. Process is carried out at ethylene pressure less than 2.5 MPa.

EFFECT: method for production of target product of increased yield.

10 cl, 1 tbl, 3 dwg, 17 ex

FIELD: petrochemical processes.

SUBSTANCE: narrow-range hydrocarbon stock is fed into reaction-distillation tower at a level located between lower and upper tower parts to perform isomerization and disproportionation of hydrocarbons. Reaction mixture is maintained in vapor-liquid equilibrium state to concentrate lighter reaction products in vapor phase and higher ones in liquid phase by means of controlling temperature profile and in-tower pressure. Higher olefins are withdrawn as bottom product and lighter olefins from the top of tower.

EFFECT: increased yield of desired product.

41 cl, 4 dwg, 5 ex

FIELD: regeneration of heat and extraction of impurities.

SUBSTANCE: the invention is pertaining to the method of regeneration of heat and extraction of impurities from the area of the heat-producing reaction in the fluidized flow, conducted for conversion into light olefins of oxygenates present in the flow of the oxygenate (oxygen-containing) raw. raw. The offered method includes the new system of a two-stage quick chilling intended for extraction at the first stage of water from the outgoing from the reactor flow and regeneration of heat of this flow for the purpose, at least, of the partial evaporation of the raw flow due to indirect heat-exchange between the oxygenated raw and the flow of the upper product of the first stage or the flow of recirculation of the first stage. The flow of purification being withdrawn from the first stage, contains the large share of impurities and the high-boiling oxygenates. In the second stage besides conduct extraction of water from the products flow containing light olefins, and produce the flow of the purified water, which requires only the minimum evaporation of the water for production of the water flow of the high degree purification. The method allows to concentrate the impurities in a rather small flow and ensures the significant saving of power and money resources at production of a flow of the vaporous raw guided into the area of realization of the heat-exchange reaction in the fluidized flow.

EFFECT: the invention ensures concentration of the impurities in a rather small flow and the significant saving of power and money at production of the flow of the vaporous raw directed into the area of realization of the heat-exchange reaction in the fluidized flow.

19 cl, 3 tbl, 4 dwg, 5 ex

The invention relates to the field of production of olefinic hydrocarbons obtained from paraffin hydrocarbons by dehydrogenation in a fluidized bed of catalyst and used for the synthesis of isoprene, ethers or other organic products and can be used in the petrochemical industry

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to methods for preparing catalyst precursors and group VIII metal-based catalysts on carrier, and to a process of producing hydrocarbons from synthesis gas using catalyst of invention. Preparation of precursor of group VIII metal-based catalyst comprises: (i) imposing mechanical energy to mixture containing refractory oxide, combining catalyst precursor with water to form paste comprising at least 60 wt % of solids, wherein ratio of size of particles present in system in the end of stage (i) to that in the beginning of stage (i) ranges from 0.02 to 0.5; (ii) mixing above prepared paste with water to form suspension containing no more than 55% solids; (iii) formation and drying of suspension from stage (ii); and (iv) calcination. Described are also method of preparing group VIII metal-based catalyst using catalyst precursor involving reduction reaction and process for production of hydrocarbons by bringing carbon monoxide into contact with hydrogen are elevated temperature and pressure in presence of above-prepared catalyst.

EFFECT: increased catalytic activity and selectivity.

12 cl, 1 tbl, 3 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: invention relates to synthesis of C5-C100-hydrocarbons from CO and H2, which catalyst contains carrier based on alumina prepared from gibbsite-structure aluminum hydroxide and cobalt in concentration of 15 to 50%. Carrier is prepared by mixing dry cobalt compound with dry gibbsite-structure aluminum hydroxide at cobalt-to aluminum molar ratio between 1:1 and 1:30, followed by calcination, impregnation (in two or more steps) with aqueous cobalt salt solution, and heat treatment. Invention also discloses process of producing C5-C100-hydrocarbons using above catalyst.

EFFECT: increased selectivity of catalyst regarding production of high-molecular hydrocarbons at reduced yield of methane.

7 cl, 1 tbl, 10 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: petroleum chemistry, chemical technology.

SUBSTANCE: method involves carrying out the preparing synthesis gas by the gaseous oxidative conversion of natural gas with air oxygen, catalytic conversion of synthesis gas to a catalyzate followed by its cooling and separating and feeding a liquid phase into reactor for synthesis of gasoline. For aim reducing the cost of manufacturing catalytic preparing methanol is carried out in the synthesis reactor wherein methanol is fed into reactor for preparing high-octane components of gasoline that are stabilized and separated for liquid components and fatty gas that is fed into reactor for preparing oligomer-gasoline. Then liquid components from reactors wherein high-octane components of gasoline and oligomer-gasoline are prepared and then combined, and the mixture is stabilized. Water formed in all synthesis reactions after separating is removed separately, combined and fed to the fresh water preparing block and formed nitrogen is fed for storage with partial using in technological cycle and in storage of synthetic fuel. The unreacted depleted synthesis gas from block wherein methanol is prepared is used for feeding methanol into reactor sprayers for preparing high-octane component of gasoline, and unreacted gases from reactor for preparing oligomer-gasoline are fed into generator for synthesis gas. Also, invention claims the device for realization of the method. The device consists of blocks for preparing synthesis gas, catalytic conversion of synthesis gas to catalyzate and preparing gasoline and made of two separate reactors for preparing high-octane additive of gasoline and oligomer-gasoline. The device is fitted additionally by block for preparing fresh water and nitrogen collector. The reactor sprayers are connected with intermediate capacity for collection of methanol and with reactor for synthesis of methanol and block for preparing methanol, and reactor for preparing oligomer-gasoline is connected pneumatically with block for preparing synthesis gas. Invention provides the development of method for the combined preparing the fuel and fresh water.

EFFECT: improved preparing method.

2 cl, 6 dwg, 2 ex

FIELD: petrochemical process catalysts.

SUBSTANCE: preparation of crusted metallic catalyst comprises: (i) applying suspension containing diluent, catalytically active metal selected from cobalt and ruthenium groups, and optionally first refractory element (atomic number at least 20) oxide onto surface of carrier particles to form wet coating and (ii) removing at least part of diluent from wet coating, said suspension containing at least 5% by weight of catalytically active metal based on the weight of calcination residue, which would result after drying and calcination of suspension. Crusted metallic catalyst itself and hydrocarbon production process are also described.

EFFECT: simplified catalyst preparation technology, improved physicochemical properties of catalyst as well as selectivity thereof, and increased productivity of hydrocarbon production process.

10 cl, 1 tbl, 3 ex

FIELD: industrial inorganic synthesis and catalysts.

SUBSTANCE: invention provides ammonia synthesis catalyst containing VII group and group VIB metal compound nitrides. Ammonia is produced from ammonia synthesis gas by bringing the latter into contact with proposed catalyst under conditions favoring formation of ammonia.

EFFECT: increased ammonia synthesis productivity.

8 cl, 2 tbl, 19 ex

FIELD: industrial organic synthesis catalysts.

SUBSTANCE: in order to increase CO-into-hydrocarbons conversion, invention provides alumina-supported catalyst containing 10-20% active Co component (calculated as CoO), 0.1-1.0% promoter F, and 0.3-1.0% platinum group metal or first transition series metal promoters or mixtures thereof.

EFFECT: increased CO conversion.

2 tbl, 8 ex

FIELD: petroleum chemistry, organic chemistry, chemical technology.

SUBSTANCE: method involves contacting a mixture of carbon monoxide and hydrogen at increased temperature and pressure with a catalyst comprising manganese and cobalt on a carrier wherein cobalt, at least partially, presents as metal and catalyst comprises also inorganic phosphate in the amount at least 0.05 wt.-% as measure for elementary phosphorus relatively to the catalyst weight. Also, catalyst can comprise vanadium, zirconium, rhenium or ruthenium additionally. Method provides selectivity in formation (C5+)-hydrocarbons and decrease in formation of CO2.

EFFECT: improved preparing method.

7 cl, 1 tbl, 2 ex

FIELD: chemical industry; conversion of synthesis gas into alcohols and hydrocarbons.

SUBSTANCE: proposed catalyst contains the following constituents, mass-%: active component in terms of CO; promoter-fluorine, 0.1-1.0; the remainder being carrier-aluminum oxide.

EFFECT: enhanced conversion of CO.

1 dwg, 2 tbl, 6 ex

FIELD: petrochemical processes.

SUBSTANCE: hydrocarbons are produced via contacting synthesis gas with catalytic composition consisting of mixture of iron-containing Fischer-Tropsch synthesis catalyst and acid component at elevated pressures and temperatures and specified iron-containing catalyst reduction conditions. Specifically, said iron component is a mixture of neodymium and cerium silicates at weight ratio between 1:9 and 9:1 and weight ratio of acid component to iron-containing catalyst ranges from 1:1 to 6:1.

EFFECT: increased selectivity and productivity of catalyst and reduced level of aromatic hydrocarbons in product.

3 cl, 1 tbl, 15 ex

FIELD: hydrocarbon manufacturing.

SUBSTANCE: natural gas is brought into reaction with vapor and oxygen-containing gas in at least one reforming zone to produce syngas mainly containing hydrogen and carbon monoxide and some amount of carbon dioxide. Said gas is fed in Fisher-Tropsh synthesis reactor to obtain crude synthesis stream containing low hydrocarbons, high hydrocarbons, water, and unconverted syngas. Then said crude synthesis stream is separated in drawing zone onto crude product stream containing as main component high hydrocarbons, water stream, and exhaust gas stream, comprising mainly remained components. Further at least part of exhaust gas stream is vapor reformed in separated vapor reforming apparatus, and reformed exhaust gas is charged into gas stream before its introducing in Fisher-Tropsh synthesis reactor.

EFFECT: increased hydrocarbon yield with slight releasing of carbon dioxide.

7 cl, 3 dwg, 1 tbl, 5 ex

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