Catalyst, method of its preparation (versions) and process of hydrodeoxygenation of oxygen-organic products of biomass fast pyrolysis

FIELD: chemistry.

SUBSTANCE: invention is referred to the area of hydrocarbons preparation by catalytical hydrodeoxygenation of products of fast pyrolysis of a biomass and working out of the catalyst for this process. The catalyst of oxygen-organic products hydrodeoxygenation of fast pyrolysis of lignocellulose biomasses, containing either precious metal in amount of no more 5.0 wt % or containing nickel, or copper; either iron, or their combination in a non-sulphide restored shape in amount of not more than 40 wt % and transitive metals in a non-sulphide shape in amount of not more than 40 wt %, carrying agent - the rest, is described. Three variants of the catalyst preparation method, providing application of transition metals on the carrying agent by a method of impregnation of the carrying agent solutions of metal compounds are described, or simultaneous sedimentation of hydroxides or carbonates of transition metals in the presence of the stabilising carrier, or the catalyst is formed by joint alloying/decomposition of crystalline hydrate nitrates of transition metals together with stabilising components of zirconium nitrate type. The process of oxygen-organic products hydrodeoxygenation of a biomass fast pyrolysis is performed using the above described catalyst in one stage at pressure of hydrogen less than 3.0 MPa, temperature 250-320°C.

EFFECT: increase stability in processing processes of oxygen-containing organic raw materials with the low content of sulphur, and also soft conditions of process realisation.

10 cl, 12 ex, 2 tbl

 

The invention relates to the field of production of hydrocarbons by catalytic hydrodeoxygenation products of fast pyrolysis of biomass and catalyst development for this process.

It is known that in the fast pyrolysis of biomass, the yield of liquid products reaches 75% by weight, which is considered as a renewable alternative to oil and gas fuel. High yield of liquid biofuels in fast pyrolysis is provided by thermal shock (heating rate 1000-10000°C/sec), low contact time (˜1 sec) and rapid cooling of the pyrolysis products. The produced liquid fuel has a lower calorific value than diesel fuel (40% of diesel), higher viscosity, acidity and unstable due to the high water content (up to 30-40%) and oxygen in the organic component. This limits the use of biofuels, but the use of catalysts opens up the possibility of refining of biofuels by the process of catalytic hydrodeoxygenation at which oxygen is removed from the organic component in the form of water [Huber, G.W.; Iborra, S.; Corma, A., Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering, Chem. Rev. (Review; 2006; 106(9); 4044-4098]. Liquid pyrolytic biofuels, or the so-called biodiesel, has a complex composition, which includes derivatives of sugars, alcohols, ethers, carboxylic acids, and f is NOlow. It should be noted that derivatives of phenol type anisole, guaiacol, METHYLPHENOL have the lowest reactivity in the reaction of catalytic hydrodeoxygenation.

Usually in the process of hydrodeoxygenation time biodiesel use sulfatirovanne Ni-Mo or Co-Mo catalysts for Hydrotreating petroleum fractions [Furimsky E., Catalytic Hydrodeoxygenation, Applied Catalysis A: General, 2000, 199, 147-190]. Direct their purpose, these catalysts have found wide application for hydrobromide hydrocarbons from oil and coal-chemical origin, the main function of which is to remove from the feedstock sulfur.

There are many solifidian deposited Ni-Mo and Co-Mo Hydrotreating catalysts [US 2007090024, C10G 45/00, 26.04.2007; KR 20070005727, C10G 45/08, 10.01.2007; EP 1762606, C10G 45/08, 14.03.2007; JP 2006346631, B01J 27/19, 28.12.2006; US 2007010682, C07C 51/43, 11.01.2007; EP 1737933, C10G 45/08, 03.01.2007; JP 2006306974, 10G 45/04, 09.11.2006; EN 2052285, B01J 21/04, 20.01.1996], in which their activity and stability is governed by the method of preparation, the introduction of the promoter, the stabilizing ligands of the active component or predecessor.

A well-known example of the use of such solifidian desulfurization catalysts in the processes of hydrodeoxygenation products of fast pyrolysis of biomass, primarily crushed wood [US 4795841, SW 51/00, 03.01.1989], which uses either Ni-catalyst, or solifidian the th Co-Mo/Al 2About3-catalyst. Biodiesel hereroense in the presence of Ni-catalyst at 250-310°and a hydrogen pressure of 14 MPa. When space velocity time biodiesel (LHSV) of 0.32-0.45 and h-1the oxygen content in the liquid drops from 45 to 20-25% by weight. Using a Co-Mo catalyst achieves a similar result with 270°C. However, both the catalyst is rapidly deactivated by supervivencia.

To solve coking of the catalyst hydrodeoxygenation in [Elliott, D.C.; Baker E.G. "Hydrotreating biomass liquids to produce hydrocarbonfuels". In: Energy from biomass &wastes X, pp.765-784. IGT, Chicago: 1986] proposed a two-stage processing time biodiesel. In the first phase of Ni-catalyst or sulpicianus Co-Mo catalyst hydrasuit biodiesel at 14 MPa and low temperatures of 250-300°obtaining a stable liquid mixture of hydrocarbons with oxygen 26-27%. At this stage, aliphatic and aromatic oxygen-containing compounds lose some oxygen groups and these compounds lose their ability to cure at higher temperatures. This is the effect of stabilization. In the second stage, the mixture is treated with hydrogen at 14 MPa and a temperature of 350°in the presence of sulfatirovannah Co-Mo/Al2About3-catalyst to reduce oxygen content to 2-3% by weight. In ductopenia the om process sulpicianus catalyst has greater stability, because the acidity of the liquid after the first stage is reduced, which is a positive factor, since it γ-Al2About3dissolved in an acidic environment.

The known method of non-isothermal hydrodeoxygenation products of fast pyrolysis of wood in the presence of solifidian desulfurization catalysts. In this case, biojidkosti served in the flow reactor, which implements the gradient of temperatures from 250 to 300°With up to 380-400°C. At the initial stage, at low temperatures there is a partial deoxygenate policelerdir organic compounds - derivatives of catechol, guaiacol - to phenol derivatives. Thus, biojidkosti stabilized and when the temperature is not polymerized and not sakakawea catalyst. In addition, biojidkosti is a complex mixture of oxygenated compounds with different reactivity and to improve yield deoxygenating products and optimization of hydrogen absorption of non-isothermal mode hydrodeoxygenation also has a positive effect. However, when the hydrogen pressure 14 MPa, and a LHSV=0,1-0,12 h-1the yield of gasoline fraction does not exceed 22-25%. Used sulfatirovanne Co-Mo/Al2O3-catalysts nevertheless lose sulfur recovered and cossutta with loss of activity in reallivepreacher.com.

Known catalyst hydrodeoxygenation of bentolila to phenol [US 7038093, SS 37/00, 02.05.2006], which is used in the integrated process for the production of phenol from benzene with the conversion of by-products - benzodia. The catalyst hydrodeoxygenation is either sulfatirovanne system type Ni, W, Co-Mo, Ni-W, Fe-Mo, Ru-Mo, Co-Mo-P, Ni-Mo-P, Co-W-Mo, Co-W-Mo-P, or systems based on noble metals, namely Pt, Pd, Pt-Zn, Pt-Re, Pt-Ni, Pt-Se, Pt-Sn, Pt-Ge, Pt-Pb, Pd, Pb, Pd-Sn. Despite a wide range of inventive catalysts hydrodeoxygenation, in the patent is the only example of the use of sulfatirovannah Co-Mo-P catalyst (Angel-hard ESCATT H-60), in the presence of at 450°and LHSV=1,2 h-1in excess hydrogen (HH2=2.5 MPa) bentolila turn into a phenol with a selectivity of 97%. It should be noted that the process of hydrodeoxygenation goes only to phenol, which is more stable in this process than bentolila.

Known method of hydrodeoxygenation depolimerizovannogo lignin, which is a mixture of mono-, di-, trialkylamine phenols and methoxyphenols with minor inclusions With7-C11alkyl benzenes and alkanes [US 5959167, C10G 47/00, 28.09.1999]. The elemental composition depolimerizovannogo lignin, wt.%: WITH 78,46; H 8,54; 0,08 N; S 0,05; 12,87. Hydrodeoxygenation carried out in two stages. First depolimerizovannogo lignin hydronaut in AB is Olave in the presence sulfatirovannah Co-Mo/γ -Al2About3-catalyst when 350-385°and a hydrogen pressure of 13 MPa with LHSV=2.5 h-1. The catalyst contained 2.5 to 6 wt.% cobalt and 7-10 wt.% molybdenum. After the first stage are formed mainly of mono-, di-, trialkylsilyl with some inclusion of paraffins C5-C12and alkyl benzenes With10. Their yield was 93% of theoretically possible. In the second stage, the mixture of hydrocarbons treated in an autoclave at 350-390°and a pressure of 13 to 20 MPa in the presence of solifidian catalytic systems with MMo formula/SiO2-Al2O3or MW/SiO2-Al2O3where M=Co, Ni, Ru, Ir, Pt, Fe, Rh, Pd, Cr and Re. At LHSV=1.5 h-1alkylated benzenes quantitatively converted into the corresponding alkylcyclohexane and alkylcyclopentanes, as well as linear and non-linear alkanes, which are components of gasoline fractions. Thus, the catalysts used in the second stage, are actually catalysts for hydrocracking, responsible for the hydrogenation of aromatic rings and erection cycle. The disadvantages of this method include high temperature process. The fact that at temperatures above 300°in parallel With hydrodeoxygenation flows through the polycondensation of polyphenols, which leads to the formation of resins and deactivation of the catalyst. It should also be noted that the PCI-e slot centers γ -Al2About3and aluminosilicate lead to rapid coking of the catalyst at elevated temperature.

Closest to the claimed technical essence and the achieved effect is a method of two-hydrodeoxygenation depolimerizovannogo lignin obtained by the alkaline hydrolysis of lignin at 230-250° [WO 2006119357, SS 7/148, 09.11.2006]. As with the previous example depolimerizovannogo lignin is a mixture of mono-, di-, trialkylamine phenols, biphenols and methoxyphenols with minor inclusions With7-C11alkyl benzenes and alkanes. First, the so-called stabilization stage is partial hydrodeoxygenation depolimerizovannogo lignin at low temperatures 200-300°and a hydrogen pressure of 3.5-14 MPa. For the stabilization stage was used sulfatirovanne catalysts M-Mo/ Support, where M=Co, Fe, Cr, Ru, Re, Pt; Support = γ-Al2About3, SiO2or carbon media, and combinations thereof. The catalysts are prepared by impregnation of the carrier, followed by drying, calcining and solifidianism gas mixture of H2S/H2at 350-450°C. And to prevent coking Al2About3was modified by neutralization with alkali surface acid sites. The highest activity and selectivity to the formation of the dryer the crystals showed deposited on a carbon carrier sulfatirovanne catalysts M-Mo/C, where M=Rh, Ru and Pt. It is noted that carbon carriers have the additional advantage of Al2About3that is the ease of extraction of precious metals from the deactivated catalyst by burning the carbon substrate. The use of these catalysts allowed for 15 min to reach 95% conversion of methoxyphenols and benzodia in the corresponding phenol derivatives with one atom of oxygen. The second stage of hydrobromide to obtain alkyl benzenes, branched paraffins and alkyl naphthenes can be conducted either as a single stage or as a combination of two separate reactions - hydrodeoxygenation and hydrocracking - at elevated temperatures 320-450°C. as catalysts of hydrodeoxygenation was primarily used sulpicianus Co-Mo/Al2About3the catalyst, as well as its modification type M-Mo/γ-Al2About3where M=Ru, Re, Cr or Fe (as well as combinations with). The hydrocracking catalysts differed from the catalysts of hydrodeoxygenation the use of more acidic media, such as aluminosilicate, and the use of nitrides of V, Mo, Ti. At pressures 7-15 MPa product of the second stage of hydrobromide is a mixture of alkyl benzenes, branched paraffins, as well as a certain number of fractions of high molecular weight alkyl naphthenes with abimaterjale oxygen 5%.

A disadvantage of the known catalysts of hydrodeoxygenation is that the catalysts are unstable when deoxygenation liquid products processing of biomass, since the catalysts lose sulfur and deactivated, and biojidkosti unlike oil has in its composition a sufficient amount of sulfur required for reactivation of the catalyst. To improve the stability solifidian catalysts in the conduct of these processes to source raw materials add sulfur compounds of the type H2S or thiophene. In addition, as noted above, for effective hydrodeoxygenation of methoxyphenols and benzodia necessary to carry out the process in two stages: first at low temperature (up to 300° (C) to phenolic derivatives, and then at higher (above 300° (C) to benzene derivatives. It should also be noted that to achieve high degrees of deoxygenation necessary to conduct the process at elevated hydrogen pressures (up to 12-14 MPa), resulting in a significant increase in the cost of products hydrodeoxygenation bioliquids.

The invention solves the problem of creating nesulfatirovannah catalyst for the process of hydrodeoxygenation coloradoradiesse compounds, including products of fast pyrolysis of biomass, with achievement levels of deoxygenation not less than 95% at more than the mild process conditions (lower temperature and hydrogen pressure).

The problem is solved by catalyst hydrodeoxygenation coloradoradiesse products of fast pyrolysis of lignocellulosic biomass, which is a complex composite containing a noble metal in an amount of not more than 5 wt.%, or Nickel, or copper, or iron, or a combination of disulfides restored form in an amount of not more than 40 wt.%, transition metals in disulfides oxide form in an amount of not more than 40 wt.% and the media.

The noble metal is chosen from the group of Rh, Ru, Pt, Pd.

The transition metal in disulfides oxide form chosen from the group of Co2About3, ZrO2CeO2, TiO2, Cr2O3Moo2WO2, Ws, MnO2.

The carrier is chosen from the group: δ-, θ-, α-Al2About3, SiO2, superagency SiO2carbon media, ZrO2SEO2, TiO2.

The composite catalyst is in the activated state contains a noble metal is not more than 5 wt.%, or transition metals not more than 40 wt.% in restored condition, which are responsible for activating hydrogen, and not more than 40 wt.% oxide of the transition metal of variable valency, responsible for the activation of oxygen-containing organic compounds. The surface of the carrier, selected from the group δ-, θ, α-Al2About3, SiO2, superagency SiO2, coal is natural media ZrO2SEO2, TiO2generally has a sour nature to prevent unauthorized cracking of hydrocarbons and coking of the catalyst.

The task is also solved by a method of preparation of the catalyst of hydrodeoxygenation, which are at least three ways.

The first option is using the multiple impregnation of capacity as follows: prepared medium is dried at 100-120°With, impregnated with a water-soluble salts of the transition metals, dried at 100-120°C, calcined at 400-550°before the formation of the corresponding oxides. The impregnation procedure is repeated as many times as required. In the case of applying multiple components impregnation of each component is carried out either sequentially or simultaneously with other components. Application of a salt of the noble metal if necessary, conduct impregnation in capacity in the last turn.

The second option is by the method of successive or simultaneous precipitation of hydroxides or carbonates of transition metals in the presence or without the media as follows: solutions of water-soluble salts of transition metals is alkalinized by hydroxides or carbonates of alkali metals or ammonia in the presence of the carrier, or without it. The sediment age at a temperature of 20-90°With 10-48 h in the mother solution. The precipitate is filtered off and washed until neutral environment. After drying the resulting composite is calcined to 500-550°C. Noble metal if necessary, is applied by impregnation in capacity on the previously formed composite.

The third option is a method of joint fusion/decomposition of the nitrates of transition metals as follows: solid crystalline nitrates of the respective transition metal is mixed with a stabilizing additives of the type nitrate zirconium, cerium, aluminum or aluminum hydroxide. The mixture is heated to the melting point of the mixture. Next, the temperature for 2-3 h increased to 300-350°C and maintained at the final temperature for 2-4 hours

Prepared for each of the above three variants of the method of the catalysts before the target process is activated by heating in a stream of hydrogen containing gas to the process temperature and keeping at finite temperature for 2 hours

The task is also solved by way of the process of hydrodeoxygenation oxygen-containing organic compounds, including products of fast pyrolysis of biomass at a temperature of 200 to 300°and a hydrogen pressure of 1.0-2.5 MPa with a bulk velocity (LHSV) oxygen-containing liquid (QL), 0.3-2.0 ml QL/ml cat/h, in the presence of the catalyst described above.

The technical result is glycaemia in high activity claimed nesulfatirovannah catalysts, allowing the process of hydrodeoxygenation oxygen-containing compounds, including liquid products of fast pyrolysis of biomass at lower temperature and pressure of hydrogen than in the presence solifidian catalysts specified in the prototype.

The process of hydrodeoxygenation carried out in reactors of the following type:

- flow fixed bed of catalyst and gaseous state of initial reagents and reaction products;

three - phase reactor with a fixed catalyst bed and downward parallel phases;

autoclave with intensive mixing of the catalyst in the liquid phase coloradorockies.com component.

Analysis of the products of hydrodeoxygenation in the gas and liquid phases carried out by gas chromatography on a gas chromatograph "Chromos-1100" using capillary column ZB-1, the stationary phase is 100% dimethylpolysiloxane 30 m × 0.32 mm × 0.25 μm; ZB-5, the stationary phase 5% phenyl+95% dimethylpolysiloxane 30 m × 0.32 mm × 0.25 μm; ZB-FFAP stationary phase - nitroterephthalic acid modified polyethylene glycol, 30 m × 0.32 mm × 0.5 µm and nozzle coal column.

The degree of deoxygenation (HDO) is determined as follows:

where- the total number of moles, not with the holding of the oxygen reaction products, - the total number of moles of all the reaction products.

The invention is illustrated by the following examples and tables.

Example 1 (I-variant of the preparation of the catalyst).

Carbon or oxide carrier selected from a number: γ-, δ-, θ; α-Al2About3, SiO2, superagency SiO2carbon media, ZrO2CeO2, CoSiO3(table 1), with a particle size of 1.5-2 mm, dried at 100-120°during the night, impregnate, depending on the type of catalyst solution of the nitrates of the transition metals, selected from the group of Co, Mn, Zr, CE, V, Cr, or molybdate or ammonium tungstate, dried at 100-120°C for 10-12 h, calcined at a temperature of 400-550°C, preferably at 450-500°C. Subsequent impregnation with dryers and progulkami carried out if necessary to achieve these mass percent coating of transition metals on the carrier. Application of a salt of a noble metal is carried out in the last turn similar method single impregnation. The resulting composite restore in the current of argon and hydrogen (volume ratio Ar:H2=1:1) by raising the temperature to 300°With a speed of 10°C/min and keeping the catalyst at finite temperature for 2 hours to skip a Number of hydrogen is taken in excess otnositel the number, necessary to restore the active component of the catalyst.

The catalyst in 10 ml of experience in a flow reactor at a hydrogen pressure of 1.0 MPa, a temperature of 300°With the current H23 l/h and Ar 3 l/h in the reaction of hydrodeoxygenation anisole with volumetric feed rate of anisole (LHSV) of 0.3 h-1.

The activity of the catalyst and the degree of deoxygenation anisole are shown in table 1.

Table 1
The activity of the catalysts based on noble metals, prepared by impregnation, in the reaction of hydrodeoxygenation anisole at a temperature of 300°C, 1.0 MPa N2and LHSV=0,3 h1
No.CatalystThe Mac.% applying metalCooking methodThe conversion of anisole %The degree of deoxygenation, %
1Rh-CoO/θ-Al2About30,5/152 impregnation With+1 Rh impregnation9875
2Rh/γ-Al2About31,51 impregnation of Rh410
3Rh-CoO/SiO22/203 impregnation With+1 Rh impregnation9981
4Rh/SiO20,51 impregnation of Rh5330
5Rh/CoSiO311 impregnation of Rh8279
6Rh/ZrO20,51 impregnation of Rh10091
7Rh/CeO20,51 impregnation of Rh10094
8Pt/θ-Al2About351 impregnation of Rh6534
9Pd-MnO2/α-Al2About32/102 impregnation Mn+1 Pd impregnation7056
10Pt-V2O5/δ-Al2About31/406 impregnations V+1 Pt impregnation7344
11EN-CeO2/C1/101 impregnation CE+1 impregnation EN9577
12Rh-ZrO2/C-SiO20,5/253 impregnation Zr+1 Rh impregnation9685

Example 2 (I-variant of the preparation of the catalyst).

Carbon or oxide carrier selected from a number: δ-, θ-, α-Al2 About3, SiO2, superagency SiO2carbon media, ZrO2CeO2, TiO2(table 2), with a particle size of 1.5-2 mm, dried at 100-120°during the night, impregnate, depending on the type of catalyst with a solution of at least two of the nitrates of transition metals, selected respectively from the group of Ni, Cu, Fe, and group: Cu, Co, Mn, Zr, CE, V, Cr, or molybdate or ammonium tungstate, dried at 100-120°C for 10-12 h, calcined at a temperature of 400-550°C, preferably at 450-500°C. In the case of carbon-containing media, the calcination is carried out in an inert atmosphere. Subsequent impregnation with dryers and progulkami carried out if necessary to achieve the mass percent coating of transition metals on the carrier. Application of a salt of a noble metal is carried out in the last turn similar method single impregnation. The resulting composite restore in the current of argon and hydrogen (volume ratio Ar:H2=1:1) by raising the temperature up to 300-350°With a speed of 10°C/min and keeping the catalyst at finite temperature for 2 hours to skip a Number of hydrogen is taken in excess relative to the amount needed to restore the active component of the catalyst.

The catalyst in an amount of 5 ml of experience in flow reactor when the pressure is AI hydrogen 1.0 MPa, a temperature of 300°With the current H23 l/h and Ar 3 l/h in the reaction of hydrodeoxygenation anisole. The activity of the catalyst and the degree of deoxygenation anisole are shown in table 2.

Table 2
The activity of catalysts based on transition metals, prepared by impregnation, in the reaction of hydrodeoxygenation anisole at 300°and 1.0 MPa N2
No.CatalystThe Mac. % applying metalCooking methodLHSV, h-1The conversion of anisole %The degree of deoxygenation %
1Fe-Cu/θ-Al2About35.3/1.81 impregnation0,32221
2Ni-Cu/θ-Al2About324.2/7.33 impregnation110099
3Ni-Cu/θ-Al2About35.3/1.81 impregnation0,35644
4*Ni-Cu/C13.5/4.52 impregnation0,354731
5Ni-Cu/ZrO237.5/12.5 6 impregnation0,756459
6Ni-Cu/CeO237.5/12.56 impregnation1,59593
7Cu-CoO/δ-Al2About340/156 impregnation14533
8Ni-MnO2/SiO212/123 impregnation0,35135
9Ni-V2O5/C10/205 impregnation0,36744
10Ni-Cr2O3/TiO216/346 impregnation0,38874
11Ni-Cu-ZrO2/C-SiO25/2/152 impregnation Zr+1 impregnation of Ni-Cu0,39182
* after application of the nitrates of Ni and Cu on carbon catalyst material to restore the current H2at 350°C.

Example 3 (II variant of the preparation of the catalyst).

To a solution containing 100 g of uranyl oxide-zirconium nitrate, 140 g of uranyl nitrate Nickel and 38 g of three-hydrate of copper nitrate, add with stirring RA is creative, containing 80 g of NaOH until pH=7. Next, the precipitation age for 24 h in the mother solution, then filtered and washed with distilled water. After drying at 150°With the received composite calcined at 500°C for 5 hours the resulting composite contains, wt%: Ni 37.5, Cu 12.5, ZrO250. Before testing in the reaction of hydrodeoxygenation catalyst restore in a stream of hydrogen at a pressure of 1.0 MPa and a temperature of 300°C. the Catalyst in an amount of 5 ml of experience in a flow reactor at a hydrogen pressure of 1.0 MPa, a temperature of 300°With the current H23 l/h and Ar 3 l/h in the reaction of hydrodeoxygenation anisole, served with a bulk velocity of 1.5 h-1. The conversion of anisole is 100%, the output deoxygenating products (benzene, toluene, cyclohexane, Methylcyclopentane) is 98%.

Example 4 (II variant of the preparation of the catalyst).

To a solution containing 75 g of uranyl nitrate Nickel and 23 g of three-hydrate nitrate honey, add as a stabilizing carrier 24.5 g of cerium oxide (II) and with stirring, a solution containing 40 g of NaOH until pH=8. Next, the precipitation age for 36 h in the mother solution, then filtered and washed with distilled water. After drying at 120°With the received composite calcined at 550°C for 3 hours the received composite contains, wt.%: Ni 37.5, Cu 12.5, CeO250. The catalyst restore, as in example 3, at a temperature of 350°and experience in the reaction of hydrodeoxygenation in a flow reactor at a hydrogen pressure of 1.5 MPa, a temperature of 250°With the current H23 l/h and Ar 3 l/h At space velocity of anisole (LHSV) of 1.25 h-1the conversion of anisole reaches 99% and the degree of deoxygenation 98%.

Example 5 (II variant of the preparation of the catalyst).

To a solution containing 50 g of uranyl nitrate cerium add as a stabilizing carrier 23 g of titanium oxide (IV) and with stirring, a solution containing 30 g of NaOH until pH=8. Precipitation of cerium hydroxide, drying and calcination of the composite were carried out as in example 4. Next, to the obtained composite add a solution containing 75 g of uranyl nitrate Nickel and 23 g of three-hydrate nitrate of copper, and with stirring, a solution containing 83 g of Na2CO3. Next, the precipitation age for 24 h in the mother solution, after which further treatment is carried out as in example 4. The resulting composite contains, wt%: Ni 25.05, Cu 8.35, CeO233.3, TiO233.3. The catalyst restore, as in example 3, at a temperature of 325°and experience in the reaction of hydrodeoxygenation in a flow reactor at a hydrogen pressure of 1.5 MPa, a temperature of 250°With the current H23 l/h and Ar 3 l/h At flow rate of feed is anisole (LHSV) of 1.25 h -1the conversion of anisole reaches 99% and the degree of deoxygenation 98%.

Example 6 (III variant of the preparation of the catalyst).

50 g of uranyl nitrate cerium, 75 g of uranyl nitrate Nickel and 23 g of three-hydrate of copper nitrate mechanically mixed. The mixture is heated to the melting point of the mixture. Next, the mixture is heated to 320°2°C/min and maintained at the final temperature for 2 hours the resulting composite contains, wt%: Ni 37.5, Cu 12.5, CEO250. The specific surface of the catalyst BET 8 m2/g Catalyst restore, as in example 3, and experience in the reaction of hydrodeoxygenation as in example 4. When space velocity of anisole (LHSV) of 1.5 h-1the conversion of anisole is 97% and the degree of deoxygenation 95%.

Example 7 (III variant of the preparation of the catalyst).

100 g of uranyl oxide-zirconium nitrate, 140 g of uranyl nitrate Nickel and 38 g of three-hydrate of copper nitrate mechanically mixed. The mixture is heated to the melting point of the mixture. Next, the mixture is heated to 350°With speeds of 3°C/min and maintained at the final temperature for 3 h the resulting composite contains, wt%: Ni 37.5, Cu 12.5, ZrO250. The specific surface of the catalyst BET 12 m2/italization restore, as in example 3, at a temperature of 350°and experience in the reaction of hydrodeoxygenation in flowing react the re when the hydrogen pressure of 1.5 MPa, temperature 250°With the current H23 l/h and Ar 3 l/h At space velocity of anisole (LHSV) of 1.0 h-1the conversion of anisole is 93% and the degree of deoxygenation 90%.

Example 8

Differs from example 7 that 63 g of aluminium nitrate mechanically mixed with 140 g of uranyl nitrate Nickel and 38 g of three-hydrate of copper nitrate, the mixture is heated to 300°C. the resulting composite contains, wt%: Ni 41, 13.7 Cu, Al2About345,3. The specific surface of the catalyst according to BET of 15 m2/italization restore, as in example 3, at a temperature of 325°and experience in the reaction of hydrodeoxygenation in a flow reactor at a hydrogen pressure of 1.5 MPa, a temperature of 300°With the current H23 l/h and Ar 3 l/h At space velocity of anisole (LHSV) of 1.0 h-1the conversion of anisole is 85% and the degree of deoxygenation 87%.

Example 9

Differs from example 8 that of 23.4 g of aluminum hydroxide mechanically mixed with 140 g of uranyl nitrate Nickel and 38 g of three-hydrate of copper nitrate, the mixture is heated to 300°C. the resulting composite contains, wt%: Ni 41, 13.7 Cu, Al2About345,3. The specific surface of the catalyst BET 18 m2/, the Catalyst was tested in the reaction of hydrodeoxygenation in a flow reactor at a hydrogen pressure of 1.5 MPa, a temperature of 300°With the current H23 l/h and Ar 3 l/h At space velocity of anisole (LHSV) of 0.75 is -1the conversion of anisole is 95% and the degree of deoxygenation 94%.

Example 10.

The catalyst Ni-Cu/θ-Al2O3(table 2, experience No. 2)containing 24.2 wt.% Ni and 7.3 wt.% Cu, experience in the reaction of hydrodeoxygenation time biodiesel product from fast pyrolysis of crushed pine (VTT, Finland), which is a mixture of derivatives of phenols (APS, methoxyacetophenone), sugars, carboxylic acids, esters, aldehydes, and nitrogen-containing aromatic compounds and has the following elemental composition: 56%, N 6.5%, 37.5%, N 0.1%. Hydrodeoxygenation time biodiesel is carried out in a three phase reactor with a fixed catalyst bed and downward parallel phases at LHSV=0,1 h-1, the hydrogen pressure of 2.5 MPa and a temperature of 320°C. the Volumetric ratio of N2/biodiesel=1000. As a result, the yield of gaseous products is 12 wt.% from the original biodiesel, water 40% and 48% of hydrocarbons with an atomic ratio H/C=1,65 and oxygen content of 1.5 wt.%.

Example 11.

The catalyst from example 5 experience in the reaction of hydrodeoxygenation period of biodiesel in an autoclave with a volume of 300 ml at 3.0 MPa of hydrogen and a temperature of 300°C. the ratio of the amount biodiesel and catalyst is 10. After 1 h, the sample of the liquid phase is collected and analyzed. The volumetric ratio of N2/biodiesel = 500 (in terms of normal conditions). In resultevent gaseous products is 8 wt.% from the original biodiesel, water 41% and 51% of hydrocarbons with an atomic ratio H/C=1.5 and oxygen content of 2.5 wt.%.

Example 12.

Differs from example 9 that sulpicianus catalyst Ni-Mo/Al2O3(Albemarle Co.) experience in the reaction of hydrodeoxygenation anisole in a flow reactor at a hydrogen pressure of 1.5 MPa, a temperature of 300°With the current H23 l/h and Ar 3 l/h At space velocity of anisole (LHSV) of 0.6 h-1the conversion of anisole is 93% and the degree of deoxygenation 15%.

As seen from the above examples, the proposed catalysts allow the process of hydrodeoxygenation coloradoradiesse compounds, primarily phenolic derivatives and products of fast pyrolysis of crushed wood in mild conditions - hydrogen pressure up to 3.0 MPa and temperature range 250-320°C. Another advantage of the inventive catalytic systems is that the catalysts have desulfatirovannae nature, which improves the stability of these systems in the processing of oxygen-containing organic feedstock with low sulfur content. The above catalysts have expressed hydrogenating ability, which allows their use in hydrogenation processes in the chemical industry.

1. The catalyst hydrodeoxygenation coloradoradiesse of fast pyrolysis products of lign the cellulosic biomass, which is a complex composite containing transition metals and the carrier, characterized in that the catalyst contains a noble metal in an amount of not more than 5.0 wt.% or contains Nickel, or copper, or iron, or a combination of disulfides restored form in an amount of not more than 40 wt.% and transition metals in disulfides oxide form in an amount of not more than 40 wt.%.

2. The catalyst according to claim 1, characterized in that the noble metal is chosen from the group of Rh, Ru, Pt, Pd.

3. The catalyst according to claim 1, characterized in that the transition metal in disulfides oxide form chosen from the group of Co2About3, ZrO2CeO2, TiO2, Cr2O3, MoO2WO2V2O5, MnO2.

4. The catalyst according to claim 1, characterized in that the carrier is chosen from the group: δ-, θ-, α-Al2O3, SiO2, superagency SiO2carbon media, ZrO2CeO2, TiO2.

5. The method of preparation of the catalyst of hydrodeoxygenation coloradoradiesse products of fast pyrolysis of biomass, which is a complex composite containing transition metals supported on a carrier by impregnation of the carrier with solutions of metal compounds, followed by drying and termomaslyanym metal compounds, characterized in that when applying multiple components PROPET what each component is carried out either sequentially, either simultaneously with other components, application of a salt of the noble metal if necessary, conduct impregnation in capacity in the last turn, thermal decomposition of metal compounds is carried out after each impregnation or in an inert atmosphere at a temperature of 400-550°C, followed by reduction with hydrogen at a temperature of 300-350°or in an oxygen environment at a temperature of 400-550°C, followed by reduction with hydrogen, either directly in the environment of hydrogen at a temperature of 300-350°C.

6. The method according to claim 5, characterized in that the carrier is chosen from the group: δ-, θ-, α-Al2O3, SiO2, superagency SiO2carbon media, ZrO2CeO2, TiO2.

7. The method of preparation of the catalyst of hydrodeoxygenation coloradoradiesse products of fast pyrolysis of biomass, which is a complex composite containing transition metals, includes drying, thermal decomposition to the corresponding oxides, wherein the catalyst is formed of sequential or simultaneous precipitation of hydroxides or carbonates of transition metals in the presence of a stabilizing carrier with subsequent aging in the mother solution, filtration and recovery of hydrogen at a temperature of 300-350°C.

8. The method according to claim 7, characterized in that the stabilizing nose is tel chosen from the group: ZrO 2CeO2, TiO2carbon material.

9. The method of preparation of the catalyst of hydrodeoxygenation coloradoradiesse products of fast pyrolysis of biomass, which is a complex composite containing transition metals, characterized in that the catalyst form a fused joint/decomposition of crystalline nitrates of transition metals together with the stabilizing additives of the type nitrate zirconium, cerium, aluminum or aluminum hydroxide by heating to a temperature of 300-350°C in air, followed by reduction with hydrogen at a temperature of 300-350°C.

10. The process of hydrodeoxygenation coloradoradiesse products of fast pyrolysis of biomass using a catalyst, wherein the process is carried out in one stage at a pressure of hydrogen of less than 3.0 MPa, a temperature of 250-320°in the presence of a catalyst according to any one of claims 1 to 4, or prepared according to any one of pp.5-9.



 

Same patents:

FIELD: chemistry.

SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.

EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.

46 cl, 1 dwg

FIELD: organic chemistry.

SUBSTANCE: invention refers to enhanced method of propane and/or butanes flow separation from original hydrocarbons containing alkylmercaptan impurities by means of fractional distillation resulted in liquid phase and separated flow from column head at pressure providing that separated flow from column head containing propane and/or butanes has temperature within 50 to 100°C, including (i) addition to specified origin hydrocarbons an amount of oxygen sufficient for mercaptan oxidation, (ii) fractional distillation of produced mixture containing at least one catalyst layer oxidising mercaptans to sulphur compounds with higher boiling temperatures and (iii) separation of sulphur compounds with higher boiling temperatures as portion of distillation liquid phase.

EFFECT: improved method of propane and/or butanes flow separation from of original hydrocarbons by means of fractional distillation resulted in liquid phase and separated flow.

8 cl, 2 tbl, 1 dwg, 1 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to treatment of C5-hydrocarbons in order to remove cyclopentadiene impurities, which process may be, in particular, used in rubber production industry when producing hydrocarbon monomers applicable in stereospecific polymerization processes. Treatment of hydrocarbons is accomplished with cyclohexane in presence of organic solvent and alkali catalyst, after which C5-hydrocarbons are separated from reaction products via rectification. Organic solvent is selected from alkylene glycol monoalkyl ethers including their mixtures taken in amounts 0.5 to 5.0 wt % based on C5-hydrocarbons.

EFFECT: increased degree of cyclopentadiene extraction at lower reagent consumption.

8 cl, 1 tbl, 23 ex

FIELD: petroleum chemistry, chemical technology.

SUBSTANCE: crude alpha-olefin is heated, raw vinylidene olefins are isomerized in the presence of catalyst and alpha-olefin is separated from isomerized vinylidene olefin by rectification. Separation of alpha-olefin is carried out for at least two successive steps at similar temperatures on top of vat and reducing pressure of rectifying column at each following step. Condensed phase removing from top of the rectifying column at previous step is fed to feeding zone of the following step and the rectifying column at top and vat section is sprayed. For spraying the top section of column the condensed phase removing from the top of rectifying column at the same step is used and for spraying the vat section of column the vat liquid of rectifying column at the same step is used. Separated alpha-olefin is purified additionally from oxygen-containing impurities by adsorption up to polymerization degree of purity. Raw heating, isomerization, separation and adsorption are carried out in atmosphere in inert gas. The unit used for treatment of alpha-olefin includes reactor for isomerization of vinylidene olefins in raw, rectifying column wherein feeding zone is joined with reactor outlet and wherein alpha-olefin of high purity degree is removed from the column top. The unit includes also at least one rectifying column for additional treatment of alpha-olefin of high purity from isomerized vinylidene olefins and adsorption column for separation of oxygen-containing impurities in alpha-olefin of high purity wherein the column inlet is joined with the top outlet of the last rectifying column used for additional treatment of alpha-olefin of high purity and outlet is used for removing alpha-olefin of the polymerization purity degree. Invention provides enhancing quality of the end product.

EFFECT: improved method for treatment.

8 cl, 1 dwg, 1 ex

The invention relates to petrochemistry, namely the production of oligomers of propylene by oligomerization of propylene in phosphoroclastic catalysts and the method of purification of oligomers of propylene

The invention relates to the petrochemical industry, for production of high-purity benzene, used in the petrochemical syntheses

The invention relates to a method of purification of benzene from coke production and benzene obtained from fractions of pyrolysis oil from impurities saturated and unsaturated hydrocarbons, thiophene and carbon disulfide

The invention relates to the petrochemical industry, for the purification of benzene, obtained from a liquid hydrocarbon, C6-C7- fractions of pyrolysis oil from impurities unsaturated hydrocarbons

FIELD: chemistry.

SUBSTANCE: described is the method of obtaining unrefined 1, 3-butadiene with the help of extractive distillation from C4-fractions, which contain C4-acetylenes as the secondary components, with the use of a selective solvent. The method is achieved in a column with dividing partitions, which contains in the bottom part an evaporator, in which lengthwise there is a dividing partition, which forms the first zone, the second zone and the underlying combined zone of the column, connected along the upper flow with the extractive washing column. Supply of energy to the column with the dividing partition through the lower evaporator is regulated such that from the column with the dividing partition draw off the lower stream, which contains the solvent, saturated with C4-acetylenes, in which the portion of 1, 3-butadiene is limited with the estimation that the 1, 3-butadiene lost is economically acceptable. In this case the lower stream is submitted into the decontaminator for acetylenes, from which C4-acetylenes are removed and the purified solvent is removed from it from the lower stream.

EFFECT: increase in the periods of the operation of the device between the cleaning cycles.

11 cl, 1 tbl, 1dwg, 1ex

FIELD: chemistry.

SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.

EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.

46 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.

EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.

46 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids. The method includes the following stages: (a) contact in the oxidation reaction zone of the alkane, which contains molecular oxygen gas, not necessarily corresponding to the alkene and not necessarily water in the presence of at least one catalyst, effective with the oxidation of the alkane to the corresponding alkene and carboxylic acid, alkane, oxygen and water; (b) separation in the first separating agent at least part of the first stream of products in a gaseous stream, which includes alkene, alkane and oxygen, and a liquid stream, which includes carboxylic acid; (c) contact of the mentioned gaseous stream with the solution of a salt of metal, capable of selectively chemically absorbing alkene, with the formation of a liquid stream rich in chemically absorbed alkene; (d) isolation from the flow of the solution of salt of the metal. The invention also relates to combined methods of obtaining alkyl-carboxylate or alkenyl-carboxylate (for example vinyl acetate), moreover these methods include oxidising of alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acid, isolation of alkene from the mixture of alkene, alkane and oxygen by absorption using the solution of the salt of metal and extraction of the stream rich in alkene from the solution of the salt from metal for using when obtaining alkyl-carboxylate and alkenyl-carboxylate.

EFFECT: improved method of oxidising alkane from C2 to C4 with the obtaining of corresponding alkene and carboxylic acids.

46 cl, 1 dwg

FIELD: chemistry.

SUBSTANCE: method of separation of starting mixture (A) consisting of two or more constituents, by extractive distillation with the selective solvent (S) within dividing wall column (TKW), is proposed. The separation is performed in the dividing wall column (TKW) having a dividing wall aligned in a longitudinal direction (TW) and extending to an upper end of the column and dividing an interior of the column into first region (1), second region (2), and lower combined column region (3). The starting mixture is fed into first region (1), first top stream (B) is taken off from first region (1), and second top stream (C) is taken off from second region (2), with each of the streams having a prescribed specification. The selective solvent (S) is introduced in an upper part of first region (1) and/or in an upper part of second region (2), and flow of solvent (S1) into the first region (1) and/or flow of solvent (S2) into second region (2) are set so that each of the prescribed specifications for top streams (B, C) are met.

EFFECT: invented method of dividing mixtures is more efficient in terms of energy and solvent consumption.

6 cl, 7 dwg, 1 tbl

FIELD: organic chemistry.

SUBSTANCE: invention refers to enhanced method of propane and/or butanes flow separation from original hydrocarbons containing alkylmercaptan impurities by means of fractional distillation resulted in liquid phase and separated flow from column head at pressure providing that separated flow from column head containing propane and/or butanes has temperature within 50 to 100°C, including (i) addition to specified origin hydrocarbons an amount of oxygen sufficient for mercaptan oxidation, (ii) fractional distillation of produced mixture containing at least one catalyst layer oxidising mercaptans to sulphur compounds with higher boiling temperatures and (iii) separation of sulphur compounds with higher boiling temperatures as portion of distillation liquid phase.

EFFECT: improved method of propane and/or butanes flow separation from of original hydrocarbons by means of fractional distillation resulted in liquid phase and separated flow.

8 cl, 2 tbl, 1 dwg, 1 ex

FIELD: organic chemistry.

SUBSTANCE: invention refers to enhanced method of propane and/or butanes flow separation from original hydrocarbons containing alkylmercaptan impurities by means of fractional distillation resulted in liquid phase and separated flow from column head at pressure providing that separated flow from column head containing propane and/or butanes has temperature within 50 to 100°C, including (i) addition to specified origin hydrocarbons an amount of oxygen sufficient for mercaptan oxidation, (ii) fractional distillation of produced mixture containing at least one catalyst layer oxidising mercaptans to sulphur compounds with higher boiling temperatures and (iii) separation of sulphur compounds with higher boiling temperatures as portion of distillation liquid phase.

EFFECT: improved method of propane and/or butanes flow separation from of original hydrocarbons by means of fractional distillation resulted in liquid phase and separated flow.

8 cl, 2 tbl, 1 dwg, 1 ex

FIELD: CHEMISTRY.

SUBSTANCE: agglomerated zeolite adsorbing materials are suggested. They contain inert bonding agent based on zeolite X with Si/Al ratio within 1.15 < Si/Al ≤ 1.5 range, with at least 90% of cation exchange centres are occupied by either barium ions only or barium and potassium ions. In the latter case, fraction of exchange centres occupied by potassium may be up to 1/3 of those occupied by barium and potassium. Remaining centres are occupied by alkali or earth metals other than barium. The Dubinin volume of these adsorbing materials measured using nitrogen adsorption at 77°К after vacuum degassing for 16 h at 300°С is 0.240 cm3/g or more.

EFFECT: resulting adsorbing materials are efficient for isolation of p-xylene from mixtures of isomers of aromatic hydrocarbons in liquid or gas phase.

13 cl, 4 ex

FIELD: petrochemical processes.

SUBSTANCE: invention relates to a method for continuously separating C4-fraction by extractive distillation using selective solvent on extractive distillation column, which method is characterized by a separation barrier disposed in extractive distillation column in longitudinal direction extending to the very top of the column to form first zone, second zone, and underlying common zone. Butanes (C4H10)-containing top stream is withdrawn from the first zone, butenes (C4H8)-containing top stream is withdrawn from the second zone, and C4H6 stream containing C4-fraction hydrocarbons, which are more soluble in selective solvent than butanes and butenes, is withdrawn from underlying common zone of column.

EFFECT: reduced power consumption and expenses.

15 cl, 2 dwg, 2 ex

FIELD: petrochemical processes.

SUBSTANCE: hydrocarbon mixture obtained by extractive distillation of C4-fraction using selective solvent, which mixture contains those C4-hydrocarbons, which are better soluble in selective solvent than butanes and butenes, is subjected to continuous separation. Mixture is supplied to first distillation column, wherein it is separated into top stream, containing 1,3-butadiene, propine, and, if necessary, other low-boiling components and, if necessary, water, and bottom stream containing 1,3-butadiene, 1,2-butadiene, acetylenes, and, if necessary, other high-boiling components. Proportion of 1,3-butadiene in bottom stream of the first distillation column is controlled in such a way as to be high enough to dilute acetylenes beyond the range wherein acetylenes can spontaneously decompose. Top stream from the first distillation column is passed to second distillation column, wherein it is separated into top stream, containing propine, and, if necessary, other low-boiling components and, if necessary, water, and bottom stream containing pure 1,3-butadiene.

EFFECT: simplified process and reduced power consumption.

4 cl

FIELD: gas treatment catalysts.

SUBSTANCE: invention relates to a method for preparing catalyst and to catalyst supported by block ceramic and metallic carrier having honeycomb structure for treating internal combustion engine exhaust gases. Preparation of catalyst comprises preliminary calcination of inert honeycomb block carrier followed by simultaneously depositing at 550-800°C, on its surface, intermediate coating of modified alumina and active phase consisting of one or several platinum group metals from water-alcohol suspension including aluminum hydroxide (boehmite, AlOOH), cerium nitrate, and one or several inorganic salts of platinum group metals. Coated material is then dried and subjected to heat treatment and reduction. According to invention, aforesaid suspension contains boehmite and cerium nitrate at 1:2 ratio and further contains reducing disaccharide so that suspension has following composition, wt %: AlOOH 18-20, Ce(NO3)3·6H2O 36-40, one or several platinum group metal salts (e.g., H2PtCl6, PdCl3, or RhCl3 calculated as metals) 1.5-1.8, reducing disaccharide 5-6, and water/alcohol (between 5:1 and 10:1) the rest. Thus obtained catalyst for treating internal combustion engine exhaust gases is characterized by: specific surface area of coating 80-100 m2/g, Al2O3 content 2.5-6.5%, CeO2 content 2.5-6.5%, active phase (calculated for platinum group metals) 0.2-0.4%, and block carrier to 100%.

EFFECT: simplified technology due to reduced number of technological stages and shortened process time, and enabled preparation of high-activity catalyst.

6 cl, 1 tbl, 8 ex

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