Catalyst for hydrodeoxygenation of organooxygen products of processing plant biomass and hydrodeoxygenation process using said catalyst

FIELD: chemistry.

SUBSTANCE: invention relates to producing a catalyst and a process of obtaining hydrocarbons via catalytic hydrodeoxygenation of products of processing plant biomass, including microalgae biomass. Described is a catalyst for hydrodeoxygenation of organooxygen products of processing plant biomass, which is a complex composite containing Ni in a reduced form and other transition metals, wherein the catalyst contains up to 15 wt % P which is in the reduced catalyst in form of phosphides with general formula where: Mi is a transition metal in phosphide form, other than nickel or boron, 2≤n≤5, with atomic ratio from 0.01-99, mainly from 7 to 99, and a stabilising additive. Described is a hydrodeoxygenation process, which is carried out in a single step at hydrogen pressure of 0.5-20 MPa, temperature of 250-320°C in the presence of the catalyst.

EFFECT: high catalyst activity.

4 cl, 39 ex, 5 tbl

 

The invention relates to the field of catalyst development and process of obtaining hydrocarbons by catalytic hydrodeoxygenation products of processing of plant biomass, including biomass of microalgae.

It is known that in the interesterification of vegetable oils is obtained a mixture of the methyl esters of fatty carboxylic acids, called biodiesel. Raw material for the production of oils can also be used as the biomass of microalgae lipid fraction which contains a large amount of triglycerides, which, together with higher productivity of microalgae makes them the most promising raw material for fuel production. The interesterification reaction is carried out at rather mild conditions (atmospheric pressure, 60-100°C) and, as a rule, in the presence of homogeneous catalysts, the yield of products can reach 90 percent or more. However, the thus obtained fuel has a number of disadvantages, primarily related to a high content of coloradolance. Such disadvantages are a higher viscosity and acidity, the lower the calorific value of the produced biodiesel compared to conventional diesel fuel.

This is one of the main reasons for restricting the use of all types of biofuels, but the use of catalysts opens up the possibility of refining the habitat of the willow by the process of catalytic hydrodeoxygenation. In this process, oxygen is removed from the organic components 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], [Furimsky E. Catalytic hydrodeoxygenation. Applied Catalysis A: General, 2000, 199(2): 147-190].

The lipid fraction of microalgae produce by way of extraction, thus extracted from biomass lipid fraction may be directly subjected to the finishing process hydrodeoxygenation then get fuel.

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, C10G 45/04, 09.11.2006; EN 2052285, B01J 21/04, 20.01.1996], in which their activity and stability are regulated by way of preparation, the introduction of the promoter, the stabilizing ligands of the active component or preaches is the owner.

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, C10B 51/00, 03.01.1989], which uses either Ni-catalyst, or sulpicianus Co-Mo/Al2O3-catalyst. Biodiesel hereroense in the presence of Ni-catalyst at 250-310°C and 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 at 270°C. However, both the catalyst is rapidly deactivated by supervivencia.

In the work Senol with TCS. [Senol, O.I., Viljava, T.-R., Krause, A.O.I. Reactions of methyl heptanoate hydrodeoxygenation on sulphided catalysts // Journal of Mol. Catal. - 2007 - V.268. - N.1-2. - P.1-8], it was shown that the reaction of hydrodeoxygenation of methylheptanoic and methylhexanoate in the presence solifidian catalysts proceeds via the formation of two intermediate products: acid and alcohol in the temperature range 250°C-300°C and a hydrogen pressure of 1.5 MPa.

Under these conditions the catalytic system NiMo/γ-Al2O3showed more activity than SOMO/γ-Al2O3. Conversion of fatty acid esters in the presence of Ni/γ-Al2About3the catalyst was 67%, and at present the AI CoMo/γ-Al 2O3only 34%. The main reaction products using Ni/γ-Al2O3-catalyst were alkanes, and in the presence of SNF/γ-Al2O3formed as alkanes and alkenes. Oxygen-containing products, the authors found.

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°C 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/Al2O3the catalysts of the m is her lose sulfur, restored and cossutta with loss of activity in the reaction of hydrodeoxygenation.

Known catalyst hydrodeoxygenation of bentolila to phenol [US 7038093, C07C 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°C, LHSV=1,2 h-1in hydrogen excess (PH2=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 of C7-C11alkyl benzenes and alkanes [US 5959167, C10G 47/00, 28.09.1999]. The elemental composition depolimerizovannogo lignin, wt.%: C - 78,46; H - 8,54; N - 0,08; S - 0,05; O - 12,87. Hydra is deoxygenation carried out in two stages. First depolimerizovannogo lignin hydronaut in an autoclave in the presence of sulfatirovannah Co-Mo/γ-Al2O3-catalyst when 350-385°C and 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 benzene C10. Their yield was 93% of theoretically possible. In the second stage, the mixture of hydrocarbons treated in an autoclave at 350-390°C and a pressure of 13 to 20 MPa in the presence of solifidian catalytic systems with the formula NiMo/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°C parallel to hydrodeoxygenation flows through the polycondensation of polyphenols, which PR is leads to the formation of resins and deactivation of the catalyst. It should also be noted that the acid sites of γ-Al2O3and aluminosilicate lead to rapid coking of the catalyst at elevated temperature.

There is a method of hydrogenation of oils in the presence of Ni-Cu-catalyst, deposited by co-deposition on various media: SiO2, Al2O3, TiO2, MgO, Cr2O3[US 3743662, C11C 3/12, 03.07.1973]. Restored at 600°C the catalyst when the content of 1 wt.% oil shows maximum activity in the hydrogenation of double bonds in triglycerides of fatty acids at 200°C and 0.5 MPa H2.

Known impregnation catalysts 15-25 wt.% Ni/Al2O3or 15-25 wt.% Co/Al2O3and Cu-Cr-Ni-catalyst H14279 Degussa, which allow gidrirovanii mixture of aldehydes, ethers (for example isotridecanol formate) of carboxylic acids to alcohols in 2-3 MPa N2and 160-190°C in the liquid phase [US 7524997, C07C 29/14, B01J 23/75, 30.07.2005]. The hydrogenation mixture is only to alcohols without the formation of the corresponding alkanes.

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. Delapouite stability solifidian catalysts in the conduct of these processes to source raw materials add sulfur compounds of the type H 2S 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 (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.

A known example of the use of the method of hydrodeoxygenation coloradoradiesse products of fast pyrolysis of lignocellulosic biomass at a temperature of 200-350°C and hydrogen pressure of 0.5 to 12.0 MPa with a bulk velocity (LHSV) oxygen-containing liquid (QL), 0.3 to 6.0 ml QL/ml cat/h, in the presence of a catalyst 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 (EN 2335340, B01J 23/89, SS 7/00, B01J 37/02, 10.10.2008). This noble metal is chosen from the group of Rh, Ru, Pt, Pd, and the transition metal in disulfides oxide form selected from the GRU is PI: Co 2O3, ZrO2CeO2, TiO2, Cr2O3, MoO2WO2V2O5, MnO2. The carrier is chosen from the group of δ-, θ-, α-Al2O3, SiO2, superagency SiO2carbon media, ZrO2CeO2, TiO2. The use of the above catalyst and reaction parameters to achieve degrees of deoxygenation various oxygen-containing compounds to 96%.

Azulfidinee catalyst for the process of hydrodeoxygenation described in Kubickova with TCS. [Kubickova, I., Snare, M., Eranen, K., Maki-Arvela, P., Murzin, D.Hydrocarbons for diesel fuel via decarboxylation of vegetable oils // Catalysis Today. - 2005. - V.106. - N.1-4. - P.197-200]. The paper describes experiments on hydrodeoxygenation of telstart as model compounds in the presence of a catalyst comprising a palladium deposited on a carbon carrier. The main reaction product was heptadecan. Conversion of ester increased with increasing temperature to 360°C reached 100%, while at 300°C it was only 32%. Stearic acid was detected as an intermediate reaction product, which was also turned into n-heptadecane. The selectivity of the formation of heptadecane decreased with increasing temperature from 70% at 300°C up to 45% at 360°C.

A disadvantage of the known catalysts of hydrodeoxygenation is that these catalysts are not the residual stability and activity in the process of deoxygenation oxygen-containing compounds, including the products of pyrolysis of lignocellulose and interesterification of vegetable oils. The reason for these drawbacks is the low stability of the media at elevated temperatures and pH 2-5, which on the one hand quickly cossutta due to the presence of surface acid centers, and on the other hand the media leached, forming soluble compounds with coloradorockies.com connections. It should also be noted that during the implementation process hydrodeoxygenation in running mode, an important parameter of the catalyst is its productivity per unit volume of reactor. In this case, the content of the active component in a unit volume is the determining factor, and the use of solid catalysts with minimal content of the inert component is preferred.

Closest to the claimed technical essence and the achieved effect is the way hydrodeoxygenation with the aim of obtaining hydrocarbons from animal fats, vegetable oils, free fatty acids. The used catalyst is a complex composite containing transition metals and the carrier, characterized in that the catalyst contains at least Nickel or copper, or iron, or a combination of not more than 54,7 wt.%, as well as the noble metal in an amount of not more than 5.0 wt.%, catalysis is a torus contains, at least, transitional, other than those listed above, the metals in oxide form in an amount of not more than 40 wt.% [EN 2356629, B01J 32/00, C07C 1/00]. However, there is no reliable data about the stability of such catalysts when working with liquids with a high content of catalytic poisons and strongly acidic pH, as, for example, the biomass of algae.

The invention solves the problem of creating a stable solid catalyst for the process of hydrodeoxygenation coloradoradiesse compounds, including products extraction and transesterification of the lipid fraction of the biomass of microalgae, achieving high degrees of deoxygenation at a higher ratio substrate/catalyst.

The problem is solved by the composition of the catalyst of hydrodeoxygenation coloradoradiesse products of processing of plant biomass, which is a complex composite containing restored in the form of Ni and other transition metals, the catalyst contains up to 15 wt.% P residing in the recovered catalyst in the form of phosphides with the General formulawhere Mi- transition metal was in the form other than Nickel or boron, 2≤n≤5, with the atomic ratio offrom 0.01 to 99, predominantly, from 7 to 99, and a stabilizing additive.

The transition metal is chosen the C group: Fe, Co, Pd, Cu, Ga, In, Tl, W, Mo.

A stabilizing additive selected from the group: Al2O3, SiO2, ZrO2CeO2, TiO2, Cr2O3, MoO2WO2V2O5, MnO2or their combination, and its amount is not more than 30 wt.%.

The task is also solved by a process of hydrodeoxygenation coloradoradiesse products processing plant biomass using the above catalyst, the process is carried out in one stage at a pressure of hydrogen of 0.5 to 20 MPa, a temperature of 250-320°C.

The catalyst hydrodeoxygenation coloradoradiesse products processing plant biomass is a complex composite containing at least three different metal, one of which is Nickel and phosphorus. The catalyst to recovery is a complex structure consisting of oxide and phosphate forms of metals, phosphorus does not exceed 15 wt.%. These metals are selected from the group of Fe, Co, Pd, Cu, B, Ga, In, Tl, W, Mo. The catalyst also contains a stabilizing additive in an amount of not more than 30 wt.%, choose from a number: Al2O3, SiO2, ZrO2CeO2, TiO2, Cr2O3, MoO2WO2V2O5, MnO2. The surface of the catalyst generally has a sour nature to prevent unauthorized cracking of hydrocarbons and coking cat who lyst.

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;

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

The technical result is the high activity of the claimed nesulfatirovannah catalysts that allow the process of hydrodeoxygenation oxygen-containing compounds, including liquid products of fast pyrolysis of biomass at higher ratio substrate/catalyst.

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 oxygen-containing reaction products,- the total quantity is of the moles of all the reaction products.

The invention is illustrated by the following examples and tables.

Example 1.

For the preparation of the catalyst NiFeCuP/SiO2method the Sol-gel synthesis capacity fall asleep the appropriate amount of Nickel carbonate basic water, copper carbonate basic, iron (II) sulfate heptahydrate, fill with distilled water and the required amount of 25% aqueous ammonia solution. Next, the mixture is stirred for 4 hours After preparation of the suspension it added to the alcoholic solution of ethyl silicate. Next, the mixture is stirred for 4 hours without stopping stirring, the suspension is heated to 80°C. the Drying is terminated by the formation of viscous paste. The paste is dried in a drying Cabinet at a temperature of 120°C for 5 h to a solid state. The catalyst was calcined in a muffle furnace. The speed of temperature rise from room temperature up to 500°C is 5° in minutes

The catalyst is maintained at the final temperature for 2 hours, then cool down with the oven. Then it was treated with a solution of NH4H2PO4the necessary concentration, after which the catalyst was again dried for 8 h at 80°C and calcined at 500°C for 1 h

The catalyst in the oxide form tabletirujut in tabletmedia in tablets 10×4 mm at a pressure of not less than 3000 kg per pill.

Further, the catalyst restore in a stream of argon and bodoro is a (volume ratio Ar:H 2=1:1) by raising the temperature up to 400°C at a rate of 10°C/min and keeping the catalyst at finite temperature for 2 hours to skip a Number of hydrogen take in excess relative to the amount needed to restore the catalyst.

The catalyst (obtained composition, wt.%: 40 - Ni 10 Fe 12 - Cu, 15 - P, 23 - SiO2) in an amount of 1 year experience in an autoclave of 300 ml with intensive stirring at a pressure of podroda 20 MPa at a temperature of 320°C and the ratio of the reagent/catalyst = 40 g/g in the reaction of hydrodeoxygenation a mixture of methyl ester of palmitic acid and ethyl ester of capric acid. Conversion of a mixture of esters reaches 45%, HDO - 60%.

Example 2-5.

The catalysts prepared by the method similar to that specified in example 1, experience in the reaction of hydrodeoxygenation guaiacol, and exposed to glacial acetic acid (100% acid).

The results of studies of such systems, their activity in the reaction of hydrodeoxygenation guaiacol and change the content of metals after treatment with acetic acid are presented in table 1.

Table 1
ExampleThe catalyst with a P/Catalyst without pThe conversion of esters % The degree HDO%The composition after treatment with acetic acid
2.45*Ni 15 Cu 10P/28 SiO2568043 Ni*13 Cu 13 P/30 SiO2
52 Ni 17 Cu/31 SiO2709042 Ni 12 Cu/46,3 SiO2
3.40 Ni 19 Mo 10 P/30 SiO2628337,5 Ni 14,5 Mo 12P/36 SiO2
45 Ni 22 Mo/33 SiO2739133 Ni 15 Mo/50 SiO2
4.46 Ni 12 Fe 10 Cu 10 P/22 SiO2817043 Ni 10 Fe 8 Cu 12 P/27 SiO2
51 Ni 13 Fe 11 Cu/25 SiO2868446 Ni 12 Fe 10 Cu/32 SiO2
5.47 Ni 6 Ga 12 Cu 5 P/30 CeO27265 47 Ni 6 Ga 12 Cu 5P/30 CeO2
50 Ni 7 Ga 13 Cu/30 CeO2807340 Ni to 4.4 Ga to 11.6 Cu/44 CeO2
* here and hereinafter specified mass percent.

Example 6-18.

The catalysts prepared in a similar way (see Example 1), experience in the reaction of hydrodeoxygenation mixture of esters: methyl ester of palmitic acid and ethyl ester of capric acid.

Data on the composition, activity and selectivity of the catalysts after 1 h the reaction, as well as their specific surface area are shown in table 2.

Samples of catalysts 56% Ni 9% Co 15% P/20% Al2O3, 44% Ni-13% Co 8% W 8% P/27% TiO2and 60% Ni 3% In 10% P/27% Al2O3restored at temperatures of 900, 450 and 600°C respectively.

Example 18-21.

The catalyst contains, wt%: 59 Ni, 10 Co, 1 Pd, 4P and 26 stabilizing additive prepared by the method similar to that described in Example 1 restore in the current of argon and hydrogen (volume ratio Ar:H2=1:1) by raising the temperature up to 300°C at a rate of 10°C/min and keeping the catalyst at finite temperature for 2 hours to skip a Number of hydrogen take in excess relative to the amount necessary to reset the setting of the active component of the catalyst.

The catalyst in an amount of 0.4 g experience in a flow reactor with a fixed bed of catalyst under hydrogen pressure of 1.0 MPa, a temperature of 300°C and load LHSV=1 h-1in the reaction of hydrodeoxygenation anisole. The main products of the reaction are benzene, cyclohexane, methylcyclohexane, toluene.

Data on activity and selectivity of catalysts, as well as their specific surface area (BET) is given in table 3.

Table 3
ExampleCatalystSpecific surface area, m2/gThe conversion of anisole %The degree of HDO, %
18NiCoPd/SiO23808590
19NiCoPd/WO21007290
20NiCoPd/Al2O3868589
21NiCoPd/MnO2 817419

Example 21-27.

The catalyst containing wt.%: 45 Ni, 12 Cu, 11 Co, 4 P, and 28 of the carrier from the series: Al2O3CeO2CeO2-ZrO2, ZrO2, TiO2, SiO2, MnO2prepared by the method similar to that described in Example 1, restore in a stream of hydrogen (flow rate of hydrogen (10 l/h) by raising the temperature up to 300°C at a rate of 10°C/min and keeping the catalyst at the final temperature for 1 hours

The catalyst fraction 0.2-0.5 mm in the amount of 0.5 cm3experience in flow reactor with a fixed bed of the catalyst at the hydrogen pressure of 1.0 MPa, a temperature of 300°C and load LHSV=6 h-1in the reaction of hydrodeoxygenation mixture of esters of methylvalerate and ecalcarata.

Data on activity and selectivity of catalysts, as well as their specific surface area (BET) is shown in table 4.

54
Table 4.
ExampleCatalystSpecific surface area, m2/gThe conversion of ethers, %The degree of HDO, %
21NiCuCoP/Al2O312070
22NiCuCoP/CeO21146252
23NiCuCoP/CeO2-ZrO2727463
24NiCuCoP/TiO2ON8059
25NiCuCoP/SiO2634557
26NiCuCoP/MnO2707564
27NiCuCoP/ZrO2697676

Example 28-34.

The catalyst contains, wt%: 47 Ni, 5 Mo, 3 Co, 4P and 29 Al2O3CeO2CeO2-ZrO2, ZrO2, TiO2, SiO2, MnO2prepared by the method similar to that described in Example 1, restore in a stream of hydrogen (flow rate of hydrogen (10 l/h) by raising the temperature on the 300°C at a rate of 10°C/min and keeping the catalyst at the final temperature for 1 hours

The catalyst fraction 0.2-0.5 mm in the amount of 0.5 cm3experience in an autoclave of 300 ml with intensive stirring at a pressure of hydrogen 17.0 MPa, a temperature of 320°C and the ratio of catalyst to 45 g/g in the reaction of hydrogenoxygen mixture of esters of methylvalerate and ecalcarata.

Data on activity and selectivity of the catalyst, as well as their specific surface area (BET) are given in table 5.

Table 5.
ExampleCatalystSpecific surface area, m2/gThe conversion of ethers, %The degree of HDO, %
28NiMoCoP/Al2O31154587
29NiMoCoP/CeO21007062
30NiMoCoP/CeO2-ZrO2783023
31NiMoCoP/TiO2 1004065
32NiMoCoP/SiO2656567
33NiMoCoP/MnO2817854
34NiMoCoP/ZrO2797969

Example 35.

The activity of the catalyst containing, wt.%: 60 Cu Ni 6 5 R and 29 SiO2the reactions of hydrodeoxygenation glycerol - 1, 2, 3 - palmitate was tested in an autoclave. For the experiments we used the fraction of the catalyst is 0.2-0.5 mm in 1 cm3, a substrate 25 ml. of the reaction Temperature is 250 and 290°C, the pressure is 0.5 MPa. The feed rate of gases: Ar 15 l/h, H25 l/h

The degree of conversion after 1 h of reaction at 290°C is 90%, the degree HDO - 7 5%at 250°C, respectively, 70 and 50%.

Example 36.

Differs from example 35 so that as the substrate using palmitic acid. The degree of conversion after 1 h of reaction at 290°C at 85%degree HDO - 62%, at 250°C, respectively, 50 and 44%.

Example 37.

The reaction of catalytic hydrodeoxygenation product is tov the transesterification of the lipid fraction of microalgae is carried out in an autoclave with a volume of 100 ml. The catalyst containing wt.%: 19 Ni, 5 Cu, 4, 4 R and 68 Al2O3prepared by the method described in example 1 is introduced into the reactor in the amount of 0.9 g, reactor purge Ar, then heated to 300°C and dried catalyst for 15 minutes and Then the reactor is cooled and rinsed with hydrogen to remove traces of argon, and then pump the hydrogen pressure up to 10 ATM at room temperature, and then the reactor is heated to 400°C and regenerate the catalyst at the same temperature for 1 h After recovery of the catalyst, the reactor is cooled to room temperature, the pressure is reduced to one atmosphere. The supply substrate is carried out using a system of fluid supply under pressure, thus avoiding oxidation of the catalyst after it is restored, only serves 25 ml of the products of the transesterification of the lipid fraction of microalgae.

After the filing of the substrate in the reactor pump the hydrogen pressure of 100 ATM and the reactor heated to 350°C. the Reaction is carried out for 1 h After which the reactor is cooled to room temperature, and the products are subjected to analysis. After the reaction, the oxygen content is reduced to 7.7% (from 30% in feedstock).

Example 38.

Differs from example 25 the fact that the use of a catalyst containing, wt.%: 15 Ni, 5 Mo, 3 Co, 4 R and 73 Al2O3. After the reaction, the amount of oxygen is the substrate decreased to 8% (from 30% in feedstock).

Example 39.

Differs from example 34 so that as the substrate used is not subjected to the process of transesterification of extracted lipid fraction of microalgae. After the reaction, the oxygen content is reduced to 15% (from 40% in feedstock).

1. The catalyst hydrodeoxygenation coloradoradiesse products of processing of plant biomass, which is a complex composite containing restored in the form of Ni and other transition metals, characterized in that the catalyst contains up to 15 wt.% P residing in the recovered catalyst in the form of phosphides with the General formulawhere Mi- transition metal was in the form other than Nickel or boron, 2≤n≤5, with the atomic ratio offrom 0.01 to 99, mostly from 7 to 99, and a stabilizing additive.

2. The catalyst according to claim 1, wherein the transition metal is chosen from the group of Fe, Co, Pd, Cu, Ga, In, Tl, W, Mo.

3. The catalyst according to claim 1, characterized in that the stabilizing additive selected from the group: Al2O3, SiO2, ZrO2CeO2, TiO2, Cr2O3Moo2WO2V2O5, MnO2or their combination, and its amount is not more than 30 wt.%.

4. The process of hydrodeoxygenation coloradoradiesse food processing plant is iomass using catalyst characterized in that the process is carried out in one stage at a pressure of hydrogen of 0.5 to 20 MPa, a temperature of 250-320°C in the presence of a catalyst according to any one of claims 1 to 3.



 

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7 cl, 4 ex, 3 dwg

FIELD: process engineering.

SUBSTANCE: invention relates to catalyst for catalytic cracking, to its production and use. Proposed catalyst comprises substrate including aluminium oxide and molecular sieve with the following distribution of pores: 5-70% of pores are sized to <2 nm, 5-70% of pores are sized to 2-4 nm, 0-10% of pores are sized to 4-6 nm, 20-80% of pores are sized to 6-20 nm, and 0-40% of pores are sized to 20-100 nm, proceeding from volume of pores sized to not over 100 nm. Proposed method comprises the following stages: mixing substrate including aluminium oxide or its precursors with molecular sieve, suspending and drying said mix by spray drying. Note here that in mixing, pore expander is introduced. Note also that said expander is selected from the group including boric acid and salts of alkaline metals. Note that expander-to-substrate weight ratio makes 0.1:100-15:100 in terms of substrate weight.

EFFECT: great volume of catalyst's pores, high capability of cracking heavy oil products and high stability of coving.

25 cl, 4 tbl, 11 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a bichrysene compound of general formula (1): where R1-R18, each independently, denote a substitute selected from a group consisting of hydrogen atoms and Ar1-Ar4, each independently, denote a hydrocarbon aromatic ring group selected from a group consisting of a phenyl group, a naphthyl group, a fluorenyl group and a phenanthryl group; and the hydrocarbon aromatic ring group can have, as a substitute, an alkyl group consisting of carbon and hydrogen atoms, said carbon atoms numbering from 1 to 6, a methoxy group, an ethoxy group, a phenyl group or a naphthyl group. The invention also relates to light-emitting devices using said compound.

EFFECT: compound has satisfactory emission brightness and longevity.

10 cl, 9 ex, 4 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a bichrysene compound of general formula (1): where R1-R18, each independently, denote a substitute selected from a group consisting of hydrogen atoms and Ar1-Ar4, each independently, denote a hydrocarbon aromatic ring group selected from a group consisting of a phenyl group, a naphthyl group, a fluorenyl group and a phenanthryl group; and the hydrocarbon aromatic ring group can have, as a substitute, an alkyl group consisting of carbon and hydrogen atoms, said carbon atoms numbering from 1 to 6, a methoxy group, an ethoxy group, a phenyl group or a naphthyl group. The invention also relates to light-emitting devices using said compound.

EFFECT: compound has satisfactory emission brightness and longevity.

10 cl, 9 ex, 4 tbl, 4 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 1-butene and isobutene and/or compound(s) thereof with alcohol(s), water, or products of di- and trimerisation of isobutene from a mixture of C4-hydrocarbons, primarily containing 2-butenes, using skeletal and positional isomerisation of 2-butenes and at least rectification, characterised by that catalysed isomerisation of 2-butenes is carried out at temperature ranging from 100°C to 500°C in a common reaction zone where positional and skeletal isomerisation to 1-butene and isobutene take place, or in separate reaction zones, in one of which there is positional isomerisation to 1-butene and in the other there is simultaneous skeletal and positional isomerisation to isobutene and 1-butene; the isobutene formed is extracted from the mixture initially in form of alkyl-tert-butyl ester(s) and/or tert-butanol and/or isobutene dimers and trimers and, optionally, said compound(s) is(are) subjected to catalysed decomposition with release of isobutene, and from the stream(s) in which 1-butene and 2-butenes are predominant, a stream primarily containing 1-butene is separated by rectification and the residue, which primarily contains 2-butenes, is at least partially recycled into the zone where there is skeletal isomerisation.

EFFECT: method enables to obtain 1-butene and isobutene in a common process, which enables to cut the size of the necessary equipment and more rationally organise flow.

11 cl, 8 ex, 3 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing 1-butene and isobutene and/or compound(s) thereof with alcohol(s), water, or products of di- and trimerisation of isobutene from a mixture of C4-hydrocarbons, primarily containing 2-butenes, using skeletal and positional isomerisation of 2-butenes and at least rectification, characterised by that catalysed isomerisation of 2-butenes is carried out at temperature ranging from 100°C to 500°C in a common reaction zone where positional and skeletal isomerisation to 1-butene and isobutene take place, or in separate reaction zones, in one of which there is positional isomerisation to 1-butene and in the other there is simultaneous skeletal and positional isomerisation to isobutene and 1-butene; the isobutene formed is extracted from the mixture initially in form of alkyl-tert-butyl ester(s) and/or tert-butanol and/or isobutene dimers and trimers and, optionally, said compound(s) is(are) subjected to catalysed decomposition with release of isobutene, and from the stream(s) in which 1-butene and 2-butenes are predominant, a stream primarily containing 1-butene is separated by rectification and the residue, which primarily contains 2-butenes, is at least partially recycled into the zone where there is skeletal isomerisation.

EFFECT: method enables to obtain 1-butene and isobutene in a common process, which enables to cut the size of the necessary equipment and more rationally organise flow.

11 cl, 8 ex, 3 tbl, 2 dwg

FIELD: chemistry.

SUBSTANCE: contacting is carried out in the presence of a catalyst containing high-silica zeolite, having a ZSM-5 structure and a promoter in form of an oxide or mixtures of oxides of transition metals selected from oxides of zinc, chromium and iron at temperature in the catalyst bed of 470-630°C.

EFFECT: use of the present method increases output of aromatic hydrocarbons, increases catalyst efficiency with respect to aromatic hydrocarbons, reduces output of easily separated recyclable by-products.

1 cl, 1 tbl, 14 ex

FIELD: chemistry.

SUBSTANCE: described are lupane A-seco-triterpenoids of general formula: , where R=HCO, R1=CONHCH2CH2COOC2H2 or R=HCO, R1=thiazol-2-yl, R=R1=CONHCH2CH2COOC2H5, or R=CH2OCOCH3, R1=COOCH3 or R=CH2OCOCH2CH2COOH, R1=COOCH3 or R=CH2OCOCH2C(CH3)2COOH, R1=COOCH3 or R-CH2OCOCH2C(CH3)2CH2COOH, R'=COOCH3, which exhibit antiviral activity towards herpes simplex virus I (HSV-1, strain 1 C). Compounds with R-R1=CONHCH2CH2COOC2H5 combine antiviral activity towards herpes virus with anti-HIV activity.

EFFECT: compounds have potential in producing antiviral agents and as key intermediates in producing novel biologically active compounds.

3 cl, 9 ex, 2 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing styrene and/or substituted styrene from material containing 1-phenylethanol and 2-phenylethanol and/or substituted 1-phenylethanol and substituted 2-phenylethanol. The method involves dehydration of material in gaseous phase at high temperature in the presence of a catalyst containing aluminium oxide particles, having multimodal pore size distribution.

EFFECT: use of the present method enables to obtain styrene with sufficient activity for a long period of time.

25 cl, 2 tbl, 5 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to catalysts of hydrorefining Diesel distillates, method of obtaining catalyst and method of hydrorefining Diesel distillates in order to obtain ecologically pure Diesel fuels and can be used in oil-refining industry. Described is catalyst for the process of hydrorefining Diesel fractions, which contains as carrier composition of aluminium oxide and zeolite β, which includes, wt %: 0.25-0.85 of magnesium compounds counted per MgO, 5-15 of silicon compounds counted per SiO2, aluminium oxide - the remaining part; and as active component catalyst contains, wt %: tungsten oxide WO3 - 20-25, nickel oxide - 3.8-4.1, phosphorus oxide - 1-1.5, carrier - the remaining part, with molar ratio tungsten/nickel W/Ni - 1.9-2.1 and phosphorus/tungsten P/W - 0.09-0.1. Described is method of catalyst preparation and method of hydrorefining of Diesel fractions, containing up to 30 wt % of catalytic cracking gas oil for which hydrorefining is carried out in reactor of hydropurification, loaded in layers with catalyst described above catalyst and CoMo/Al2O3 - catalyst, the latter is located in the first layer in the direction of movement, which are taken in ratio from 1:3 to 1:1.4, at temperature 340-370°C, hydrogen pressure 3.5-7.0 MPa.

EFFECT: high efficiency of hydrorefining of Diesel fraction with higher content of polycyclic aromatic hydrocarbons, nitrogen-containing and stable sulphur-containing compounds.

4 cl, 11 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing hydrogen cyanide through catalytic oxidation of starting material in ammonia medium. The oxidation method is carried out in ammonia medium of alcoholic starting material such as methanol, or nitrile starting material such as propionitrile, or mixture thereof. To form hydrogen cyanide, modified Mn-P catalyst is used, having the following empirical formula: MnaPlAbOx, where A is one or more elements K, Ca, Mo, Zn, Fe or combination thereof; a varies from 1 to 1.5; b varies from 0.01 to 1.0 and x is the total number of oxygen atoms, which is determined from the oxidation state of present elements. The invention also includes a catalyst for oxidation in ammonia medium.

EFFECT: catalyst has high activity.

13 cl, 2 tbl, 5 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a method of producing a hydrotreatment catalyst. Described is a method of producing a hydrotreatment catalyst which involves the following steps: a) at least one step for saturating a dried and/or annealed catalyst precursor containing at least one group VIII element and/or at least one group VIB element and an amorphous support using an impregnating solution consisting of at least one phosphorus-containing compound dissolved in at least one polar solvent with relative permittivity higher than 20; b) a step for maturation of said saturated catalyst precursor obtained at step a); wherein said maturation step is carried out at atmospheric pressure, at temperature ranging from ambient temperature to 60°C for maturation period of 12 to 340 hours; c) a step for drying without a subsequent step for annealing said catalyst precursor obtained at step b), wherein the drying step c) is carried out in a drying oven at atmospheric or low pressure and at temperature 50-200°C. Described is use of the catalyst obtained using the described method to carry out hydrofining and hydroconversion of hydrocarbon material.

EFFECT: high catalyst activity.

14 cl, 8 tbl, 17 ex

FIELD: chemistry.

SUBSTANCE: stable composition for application for catalyst carrier impregnation in order to obtain catalytically active solid substance includes: (A) water; (B) catalytically active metals, which are in form of and containing: (1) at least, one component, ensuring, at least, one metal of group VIB of Periodic system; and (2) at least, one component, ensuring, at least, one metal of group VIII of Periodic system, selected from group consisting of Fe, Co and Ni; and (i) said metal of group VIII is supplied with, in fact, insoluble in water component; (ii) molar ratio of said metal of group VIII and metal of group VIB constitutes approximately from 0.05 to approximately 0.45, on condition that amount of said metal of group VIII is sufficient for promoting catalytic impact of said metal of group VIB; (iii) concentration of said metal of group VIB, expressed as oxide, constitutes, at least, from approximately 3 to approximately 50 wt % of said composition weight; and (C) at least, one, in fact, water-soluble phosphorus-containing acid component in amount, insufficient for dissolving said metal of group VIII at room temperature, and sufficient for ensuring molar ratio of phosphorus and metal of group VIB from approximately 0.05 to less than approximately 0.25. Described is method of obtaining described above composition, including addition to suitable water amount of: (A) at least, one in fact water-insoluble component based on metal of group VIII, selected from group consisting of Fe, Co and Ni; and (B) at least, one in fact water-soluble phosphorus-containing acid component in amount insufficient for causing dissolution of said component based on metal of group VIII, with obtaining suspension, and combining suspension with: (C) at least, one component based on metal of VIB group; and (D) mixing of combinations (A), (B) and (C), and heating mixture during time and to temperature sufficient for formation of solution by (A), (B) and (C); and (E) adding supplementary amount of water, if necessary, in order to obtaining concentrations of solution of, at least, one said metal of group VIII, at least, one said metal of group VIB and phosphorus, suitable for impregnation of said carriers; group VIB and VIII refer to groups of periodic system of elements. Described is catalyst obtained by carrier impregnation with stable composition, suitable for hydrocarbon raw material processing.

EFFECT: increase of conversion degree of sulphur, microcarbon residue.

23 cl, 3 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: proposed catalyst is composed of 12.0-25.0% MoO3, 3.3-6.5% CoO, 0.5-1.0% P2O5, and Al2O3 to the balance. Catalyst preparation comprises one- or two-step impregnation of support with solution obtained by mixing solutions of ammonium paramolybdate, cobalt nitrate, phosphoric and citric acids taken at ratios P/Mo = 0.06-0.15 and citric acid monohydrate/Co = 1±0.1, or mixing solutions of ammonium paramolybdate and phosphoric acid at ratio P/Mo 0.06-0.15 and cobalt acetate followed by drying and calcination stages. Diesel fraction hydrodesulfurization process is carried out in presence of above-defined catalyst at 340-360°C and H2-to-feedstock ratio = 500.

EFFECT: intensified diesel fraction desulfurization.

7 cl, 2 tbl, 13 ex

FIELD: catalysts in petroleum processing and petrochemistry.

SUBSTANCE: invention relates to catalysts for extensive hydrofining of hydrocarbon stock, in particular diesel fractions, to remove sulfur compounds. Catalyst of invention, intended for diesel fraction desulfurization processes, comprises active component, selected from oxides of group VIII and VIB metals and phosphorus, dispersed on alumina support, said alumina support containing 5-15% of montmorillonite, so that total composition of catalyst is as follows, wt %: molybdenum oxide MoO3 14.0-29.0, cobalt oxide CoO and/or nickel oxide 3-8, phosphorus 0.1-0.5, and support - the balance, molar ratio Mo/Co and/or Mo/Ni being 1.3-2.6 and P/Mo 0.08-0.1. Preparation of catalyst support consists in precipitation of aluminum hydroxide and addition of montmorillonite with moisture content 55-70% to water dispersion of aluminum hydroxide in amount such as to ensure 5-15% of montmorillonite in finished product, after which resulting mixture is extruded and extrudate is calcined at 500-600°C to give support characterized by specific surface 200-300 m2/g, pore volume 0.5-0.9 cm3/g, and prevailing pore radius 80-120 Å. Catalyst preparation comprises impregnation of calcined support with complex solution of group VIII and VIB metal salts and phosphorus followed by heat treatment in air or nitrogen flow at temperature not exceeding 200°C, impregnation solution notably containing molybdenum oxide and cobalt and/or nickel carbonate at Mo/Co and/or Mo/Ni molar ratio 1.3-2.6 stabilized with orthophosphoric acid and citric acid to P/Mo molar ratio between 0.008 and 0.1 at medium pH between 1.3 and 3.5. Described is also diesel fraction hydrodesulfurization process involving passage of diesel fraction through bed of above-defined catalyst.

EFFECT: intensified diesel fraction desulfurization.

9 cl, 3 tbl, 19 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

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