Catalyst, preparation method thereof and method for single-step synthesis of propylene from ethylene

FIELD: chemistry.

SUBSTANCE: invention relates to oil and gas chemistry and specifically to catalysts and processes for synthesis of light alkenes, particularly propylene. Described is a catalyst for single-step synthesis of propylene from ethylene, containing rhenium oxide Re2O7 and nickel oxide NiO, attached to the surface of a carrier in form of borate-containing aluminium oxide with the following ratio of components in wt %: Re2O7 - 5-13; NiO - 4-8; B2O3 - 15-18; Al2O3 - the rest. Described is a method of preparing said catalyst, which involves preliminary production of borate-containing aluminium oxide by mixing a hydrate of aluminium oxide having a pseudo-boehmite structure with ortho-boric acid, drying at 120°C and calcination at 550°C in an air current for 16 hours, followed by saturation of the borate-containing aluminium oxide with an aqueous solution containing perrhenic acid and nickel nitrate, drying at 120°C and calcination at 550°C for 16 hours. Described also is a method for single-step synthesis of propylene from ethylene which involves passing a stream of pure (100%) ethylene through a fixed layer of the disclosed catalyst at temperature 40-150°C, pressure close to atmospheric pressure and mass flow rate of feeding ethylene equal to 1 h-1.

EFFECT: high efficiency of single-step synthesis of propylene from ethylene owing to high selectivity of formation and output of propylene.

3 cl, 1 tbl, 7 ex

 

The invention relates to the field of oil and gas chemistry, and in particular to catalysts and processes for the production of light-weight alkenes, in particular propylene.

In recent years, the world is increasing consumption of propylene as the source for obtaining high-quality polypropylene plastics, Acrylonitrile, acrylic acid and other valuable chemicals [J.S.Plotkin / The changing dynamics of olefin supply/demand // Catal. Today. 2005. V.106. P.10-14]. But still propylene is produced mainly as a by-product of ethylene product, in the processes of pyrolysis of light hydrocarbons [Tinsukia and other Pyrolysis of hydrocarbons. M.: Chemistry, 1987]. The elimination of commodity shortages of propylene can be arranged at the expense of its receipt of ethylene produced during pyrolysis in much larger quantities. In this regard, since the 1990s, there has been actively developed and implemented in the global industrial practice catalysts and technologies metathesis of ethylene and butenes-2 in propylene [R.Streck / Economic and ecological aspects in applied olefin metathesis // J.Mol. Catal. 1992. V.76. P.359-372; J.C.Mol / Industrial applications of olefin metathesis // J.Mol. Catal. A: Chem. 2004. V.213. P.39-45]. As catalysts for metathesis use the oxides of tungsten, molybdenum and rhenium supported on silica gel, aluminum oxide, amorphous aluminosilicates, including optionally modified by additions of zirconium oxide, zeolites, neora the systematic acids [J..Mol, .W.N.. van Leeuwen / Methathesis of Alkenes // in Handbook of Heterogeneous Catalysis. 2ndEd. Eds. G.Ertl, H.Knözinger, F.Schuth, J.Weitkamp. Wiley-VCH Verlag GmbH &Co.KGaA. Weinheim. 2008. Vol.7. P.3240-3256].

The principal shortcoming of the existing processes for the synthesis of propylene from ethylene is a multi-stage. In this advance on a separate catalyst spend the dimerization of ethylene to butene-1, butene-1 to separate the catalyst will isomerized in the butenes-2 and then a mixture of ethylene and butenes-2 are subjected to metathesis. The last two stages sometimes combine, holding them in a mixture of metathesis catalyst with the catalyst (type MgO), which provides preliminary isomerization of butene-1. Meanwhile, there is no fundamental thermodynamic constraints for the implementation of all the necessary stages of transformation of ethylene to propylene (dimerization, isomerization; metathesis) in the same conditions [X.Tang, H.Zhou, W.Qian, D.Wang, Y.Jin, F.Wei / High selectivity values Production of Propylene fron n-Butene: Thermodynamic and Experimental Study Using a Shape Selective Zeolite Catalysts // Catal. Lett. 2008. V.125. P.380-385]. Known and the corresponding polyfunctional catalysts and methods for their preparation and use for direct one-step to obtain propylene from ethylene.

By a known method [U.S. patent 3689589, 1972] the catalyst that is suitable for one-step conversion of ethylene in more high molecular weight alkenes, get, impregnating silica gel first, water is the first solution of Nickel nitrate, followed by drying at 120°C, then an aqueous solution of metavolume ammonium with subsequent drying and calcination at 600°C in air flow. In flow conditions at a temperature of about 370°C and a pressure of 2.8 MPa, the catalyst provides a degree of conversion of ethylene (X), diluted with n-heptane, 3.2%, and the selectivity of the formation of propylene (S) of 7.2 wt.%. The estimated yield of propylene (Y=X·S/100) is equal to 0.23 wt.%. The disadvantages of this method are very low activity and selectivity of catalyst performance and, accordingly, the yield of propylene.

A known method of producing a catalyst for the conversion of ethylene [U.S. patent 3728415, 1973], which includes impregnation of the alumina with an aqueous solution of heptamolybdate ammonium, drying, calcining in a stream of air at 525-550°C, then the impregnation of ammonium solution of palladium chloride, drying, calcining in air at 540°C, the reduction with hydrogen at the same temperature, again annealed in air. The finished catalyst contains 10 wt.% Moo3, 2 wt.% PdO, the rest is aluminum oxide. In flow conditions at a temperature of 35°C and atmospheric pressure, the catalyst provides a degree of conversion of pure ethylene 80,0%, the selectivity of the formation of propylene of 38.7 wt.%. The estimated yield of propylene equals 31,0 wt.%. The disadvantages of this method are the necessity of using the catalyst composition is precious the first metal palladium, the complexity of the preparation of the catalyst is necessary threefold annealing, including processing in the hydrogen flow, not high enough for practical use of the selectivity of the formation of propylene.

The closest technical result to the present invention is the rhenium oxide catalyst for metathesis of olefinic hydrocarbons, the method of its production and a method for the synthesis of propylene with its use, including only one ethylene [RF Patent 2292951, 2005, the prototype]. The catalyst is a Re2O7formed on the surface bionaturae media, which is used as gamma-alumina containing 2.0 wt.% fluorine. In the case of using a catalyst to obtain propylene only from ethylene content Re2O7it includes up to 1 wt.%. To obtain the rhenium oxide catalyst suitable for one-step conversion of ethylene to propylene, gamma-alumina containing 2.0 wt.% fluorine, impregnated with an aqueous solution of ammonium perrhenate at 20-70°C for 6 hours, dried at 110°C and carry out thermal treatment at 750°C in inert gas - argon. In flow conditions at a temperature of 125°C, atmospheric pressure and the ethylene content in the initial mixture 16-32% vol. the catalyst provides a degree of conversion of ethylene to 13.2%, electively education propylene 64,8 wt.%. The estimated yield of propylene is equal to 8.6 wt.%. The main disadvantages of the prototype are the necessity of using an inert environment upon receipt of the catalyst, obtaining propylene from diluted atlantageorgia mixture, low values of selectivity of formation and yield of propylene.

The purpose of this invention is to develop a new catalyst, which includes high-temperature treatment only available in the air, and allowing one-step synthesis of propylene of pure (100%) of an ethylene selectivity of the formation and yield of propylene over 65,0 and 8.6%, respectively.

As a solution for achieving the goal of the present invention, it is proposed the catalyst for one-step synthesis of propylene from ethylene, containing oxide of rhenium Re2O7and Nickel oxide NiO, mounted on the carrier surface, which is used bortagaray aluminum oxide, in the following ratio, wt.%: Re2O7- 5-13; NiO - 4-8;2About3- 15-18; Al2O3-the rest. Required for one-step synthesis of propylene from ethylene poly-functionality of the proposed catalyst is provided: caused by Nickel oxide NiO for the dimerization of ethylene to butene-1, acid properties bortagaray of aluminum oxide for the somersalo of butene-1 in the butenes-2 and caused by the oxide of rhenium Re 2O7for the occurrence of metathesis of ethylene and butenes-2 in propylene.

The way to get a new catalyst, the proposed one-step synthesis of propylene from ethylene, includes obtained prior bortagaray alumina by mixing hydrate of aluminum oxide pseudoboehmite patterns with orthoboric acid based on the mass ratio of In2About3:Al2O3equal to 0.25, with further drying at 120°C. and calcination at 550°C in a stream of air for 16 hours and subsequent impregnation bortagaray of aluminum oxide with an aqueous solution containing rhenium acid and nitrate of Nickel, with further drying at 120°C, annealing at 550°C for 16 hours and provide the following ratio of components in the catalyst, wt.%: Re2O7- 5-13; NiO - 4-8;2About3- 15-18; Al2O3- the rest.

The single-stage method for the synthesis of propylene from ethylene includes the transmission of a stream of pure (100%) of ethylene through the fixed layer of the proposed catalyst at a temperature of 40-150°C., the pressure is close to atmospheric, and the mass feed rate of ethylene 1 h-1.

The invention is illustrated by the following examples.

Example 1. To obtain pre-catalyst receive bortagaray alumina by mixing hydrate of aluminum oxide what I pseudoboehmite patterns and orthoboric acid based on the mass ratio of In 2About3:Al2O3equal to 0.25. The resulting mixture was dried at 120°C., and then calcined at 550°C in a stream of air for 16 hours. Received bortagaray aluminum oxide impregnated with a mixture of aqueous solutions of rhenium acid and Nickel nitrate based achievements of the contents of 10 wt.% Re2O7and 5 wt.% NiO in the finished dry catalyst. Impregnated bortagaray alumina is dried at 120°C and calcined at 550°C in a stream of air for 16 hours. According to the atomic-emission analysis, the catalyst contains about 10.8 wt.% Re2O7, 4.4 wt.% NiO, of 17.0 wt.% In2About3the rest - Al2O3.

Process one-step synthesis of propylene from ethylene spend on running the installation with a fixed catalyst bed at a pressure close to atmospheric. As raw materials use of pure (100%) ethylene, served with a mass at 1 h-1. The temperature holding process is 40°C.

In the process, the degree of conversion of ethylene reaching 16.2%. As products are formed propylene (C3H6), butenes (C4and more high molecular weight alkenes (C5+). Thus the selectivity of the formation of propylene is 71.4 wt.% against 64,8 wt.% for the prototype method. The yield of propylene is 11.6 wt.% against 8.6 wt.% for the prototype method.

Por what measures 2. Similar to example 1, but the temperature of the process one-step synthesis of propylene from ethylene is 80°C. In the process, the degree of conversion of ethylene reaches of 17.3%. As products are formed propylene (C3H6), butenes (C4and more high molecular weight alkenes (C5+). Thus the selectivity of the formation of propylene is 65,5 wt.%, the yield of propylene is 11.3 wt.%.

Example 3. Similar to example 1, but the temperature of the process one-step synthesis of propylene from ethylene is 120°C. the Selectivity of the formation of propylene makes 81.9 wt.%, the yield of propylene and 9.0 wt.%.

Example 4. Similar to example 1, but bortagaray aluminum oxide impregnated with a mixture of aqueous solutions of rhenium acid and Nickel nitrate based achievements of contents 5 wt.% R.e2O7and 5 wt.% NiO in the finished dry catalyst. According to the atomic-emission analysis, the catalyst contains a 5.1 wt.% Re2O7, 4.9 wt.% NiO, 18.0 wt.% B2O3the rest - Al2O3.

The temperature of the process one-step synthesis of propylene from ethylene is 40°C. In the process, the degree of conversion of ethylene reaches 12.5 percent. As products are formed propylene (C3H6), butenes (C4and heavier and Kenny (C 5+). Thus the selectivity of the formation of propylene 73,6 wt.%, the yield of propylene is 9.2 wt.%.

Example 5. Similar to example 4, but the temperature holding process is 80°C. In the process, the degree of conversion of ethylene reaches of 16.4%, the selectivity of the formation of propylene is 70,8 wt.%, the yield of propylene - 11.6 wt.%.

Example 6. Similar to example 4, but the temperature holding process is 150°C. the Selectivity of the formation of propylene is 87,1 wt.%, the yield of propylene to 9.5 wt.%.

Example 7. Similar to example 1, but bortagaray aluminum oxide impregnated with a mixture of aqueous solutions of rhenium acid and Nickel nitrate based achievements contents of 15 wt.% Re2O7and 10 wt.% NiO in the finished dry catalyst. According to the atomic-emission analysis, the catalyst contains 12.4 wt.% Re2O7, 8.0 wt.% NiO, 15.9 wt.% B2O3the rest - Al2O3.

The temperature of the process one-step synthesis of propylene from ethylene is 80°C. In the process, the degree of conversion of ethylene reaches 14.5%. As products are formed propylene (C3H6), butenes (C4and more high molecular weight alkenes (C5+). Thus the selectivity of the formation of propylene is 66,2 wt.% against 64,8 wt.% for fashion-Pro is atipa. The yield of propylene is 9.6 wt.% against 8.6 wt.% for the prototype method.

The Table presents the data of examples on the performance of the proposed method for one-step synthesis of propylene from ethylene, based on the use of the new catalyst and method of its production. There is presented for comparison of the characteristics of the prototype method. From the data given in the Table, it is seen that the proposed catalyst comprising an oxide of rhenium Re2O7and Nickel oxide NiO, fixed on the surface bortagaray of aluminum oxide and having the following ratio of components, wt.%: Re2O7- 5-13; NiO - 4-8;2About3- 15,8-18,2; Al2O3- else, if the temperature of 40-150°C provides high values of selectivity of formation and yield of propylene with its one-step synthesis of ethylene. The most preferred is a catalyst containing 10.8 wt.% Re2O7and 4.4 wt.% NiO, which is at a temperature of 40°C provides a degree of conversion of ethylene of 16.2% (3% higher than for the prototype method), the selectivity of the formation of propylene 71.4 wt.% (6.6% higher than for the prototype method), the yield of propylene to 11.6 wt.% (3% higher than for the prototype method). Additional advantages of the invention are able to obtain catalyst by calcination in dostupnost.moy environment and use as raw materials of pure (100%) of ethylene.

Thus, the proposed catalyst and method for producing it possible to raise the effectiveness of one-stage synthesis of propylene from ethylene and can be implemented in a typical industrial conditions caused alumina catalysts.

Table
ExampleThe catalyst composition, wt.%Process temperature, °CThe degree of conversion of ethylene, %The yield of propylene, wt.%The selectivity of the formation of products, wt.%
Re2O7NiOB2O3Al2O3With3H6With4With5+
110,84,4of 17.067,840,016,2the 11.671,422,0 6,5
210,84,4of 17.067,880,0the 17.311,365,512,322,2
310,84,4of 17.067,8120,011,09,081,911,76,5
45,1a 4.918,072,040,012,59,273,621,64,8
55,1a 4.918,072,080,016,4the 11.670,817,212,1
6 5,1a 4.918,072,0150,010,99,587,112,90,0
712,48,015,963,780,014,59,666,223,210,7
The placeholder125,013,28,664,826,88,4

1. The catalyst for one-step synthesis of propylene from ethylene, containing oxide of rhenium Re2O7fixed on the surface of the anion-modified aluminum oxide, characterized in that it further comprises a Nickel oxide NiO, as well as media use bortagaray aluminum oxide, in the following ratio, wt.%:

Re2O75-13
NiO4-8
In2About315-18
Al2O3rest

2. The method of producing catalyst for one-step synthesis of propylene from ethylene, comprising the impregnation of the anion-modified aluminum oxide in an aqueous solution of rhenium acid, drying and calcination in air flow, characterized in that bortagaray aluminum oxide is obtained by mixing hydrate of aluminum oxide pseudoboehmite patterns with orthoboric acid, drying at 120°C. and calcination at 550°C for 16 h, followed by impregnation bortagaray of aluminum oxide with an aqueous solution containing rhenium acid and Nickel nitrate, dried at 120°C. and calcination at 550°C for 16 h, in the following ratio, wt.%:

Re2O75-13
NiO4-8
B2O315-18
Al2O3rest

3. The single-stage method C the importance of propylene from ethylene, includes passing a stream of ethylene through the fixed catalyst bed, wherein the synthesis is carried out on the catalyst according to claim 1 at a temperature of 40-150°C., the pressure is close to atmospheric, and the mass feed rate of ethylene 1 h-1.



 

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8 cl, 1 tbl, 19 ex

FIELD: chemistry.

SUBSTANCE: invention relates to a catalyst for hydrodesulphurisation of naphtha, a method of preparing said catalyst and a method for hydrodesulphurisation of naphtha using said catalyst. Described is a method of preparing the catalyst for hydrodesulphurisation of naphtha and versions thereof, involving: (i) saturating a silicon oxide based support, where the support contains at least approximately 85 wt % silicon oxide and has pore volume between 0.6 and 2.0 cm3/g and average pore size between 150 and 2000 Å, (a) with an aqueous solution of a cobalt salt, (b) an aqueous solution of a molybdenum salt and at least one organic additive. The said organic additive contains at least one organic acid and at least one compound selected from a group consisting of compounds containing at least two hydroxyl group and 2-20 carbon atoms, and (poly)ethers of these compounds, to obtain a catalyst precursor; (ii) drying the catalyst precursor at temperature lower than approximately 350°C to obtain a dry catalyst precursor, and (iii) possibly sulphidation of the dry catalyst precursor, provided that the dry catalyst precursor, or catalyst, is not calcined before sulphidation or use for hydrodesulphurisation. The catalyst for hydrodesulphurisation of naphtha prepared using the method given above is described. Described also is a method for hydrodesulphurisation of naphtha, having olefin content of at least 5 wt % in terms of the weight of naphtha, involving sulphidation of the catalyst and its reaction with naphtha under hydrodesulphurisation conditions.

EFFECT: low degree of saturation of olefins while also minimising loss of octane number and achieving high hydrodesulphurisation activity.

33 cl, 1 tbl, 8 ex, 1 dwg

FIELD: chemistry.

SUBSTANCE: invention relates to general or special catalysis, particularly to methods of producing catalysts for oxidising carbon oxide and hydrocarbons and can be used in systems for reducing toxicity of exhaust gases from various technological processes, where gas released into the atmosphere contains harmful organic substances and carbon oxide. Described is a method of producing a catalytic composite coating, involving obtaining a catalytically active layer on a metal carrier via plasma sputtering of a powdered composition onto a metal carrier. An adhesion layer is deposited by sputtering a powdered composition containing the following in wt %: aluminium 3-5, aluminium hydroxide - the rest; a porous catalyst layer is deposited by sputtering a powdered composition containing the following in wt %: aluminium 3-5, chromium oxide 2-5, tungsten oxide 0.8-1.2, oxides of cerium, lanthanum, neodymium in total of 1.8-2.2, copper oxide 2-3, aluminium oxide - the rest; an activator layer is then deposited via a ion-plasma technique using two evaporators, where the said layer contains the following in wt %: copper oxide 27-34, chromium oxide 66-73.

EFFECT: higher strength of adhesion of the catalyst layer to the metal carrier, lower ignition temperature while retaining high catalytic activity.

5 cl, 3 tbl

FIELD: process engineering.

SUBSTANCE: invention relates to methods of producing catalysts intended, primarily, for ICE exhaust gas cleaning, said gases containing rare earth oxides and platinum group metals. Proposed method comprises impregnating premade inert carrier with organic solutions containing one or several compounds of rare earth elements and one or several compounds of platinum group metals, stripping of organic solvent and thermal treatment of carrier with rare earth metal oxides and noble metals deposited on its surface at 600-700°C. Organic solvents represent extracts of europium and/or cesium compounds and compounds of platinum and/or palladium mixed in ratio that allows the presence of platinum and/or palladium catalyst in solid active phase in amount of 0.5-2 wt % and europium or cesium oxide in amount of 98-99.5 wt %.

EFFECT: possibility to impregnate inert carrier in one stage that notably simplifies catalyst production and shortens process duration.

5 cl, 10 ex

FIELD: process engineering.

SUBSTANCE: invention relates to hydraulic treatment catalysts and methods of their production. Proposed method comprises: (I) using, at least, on of the following components: (A) one calcinated porous carrier; (B) catalytically active metals used in hydrocarbon hydraulic treatment, at least, one metal of VIB group of periodic table, and, at least one component including, at least, one metal of VIII group of periodic table; (C) at least, one chelate; (D) water in amount sufficient for producing solution or dispersion containing said catalytically active metals and at least, one said chelate; (II) interaction of said components (1)(A) with said solution or dispersion containing (1)(B) and (1)(C) during time interval and at temperature sufficient for mix production and impregnation of said carrier with said components (1)(B) and (1)(C) (III) to make the volume of said solution or dispersion equal to or exceeding water porosity of said carrier by separating said impregnated carrier from solution or dispersion volume that exceeds water porosity volume; and (IV) heating said impregnated carrier to above 200°C, and lower temperature and time period that may cause notable destruction of, at least, one said chelate.

EFFECT: chelated hydraulic treatment catalyst with low moisture content.

18 cl, 8 tbl, 5 ex

FIELD: process engineering.

SUBSTANCE: invention relates to production of metal-carbon compositions. Platinum catalysts represent metal-carbon compositions based on platinum nanoparticles secured on porous carbon carrier surface with metal content varying from 15 to 60 vol. %. Proposed method consists in pre-saturation of carrier surface by adsorbed complex platinum compounds that, in subsequent hydrolytic platinum deposition from solution, are converted into platinum surface oxides to initiate autocatalytic growth of nanoparticles of said oxides. Note here that deposition is carried out from solutions of the following composition: chloroplatinic acid (H2PtCl6) + alkaline agent + organic reducer, while final reduction of applied platinum is conducted in hydrogen flow at 120-250°C.

EFFECT: final catalysts with highly dispersed particles of applied metal.

3 cl, 46 ex, 8 tbl

FIELD: chemistry.

SUBSTANCE: invention relates to production of hydrofining catalysts. Described is a catalyst for hydrofining heavy petroleum cuts which contain active components: [Si·(WO3)12] in amount of 1.0-9.0 wt %; [P-(WO3)12] in amount of 1.0-9.0 wt %; [Si-(MoO3)12] in amount of 4.0-22.0 wt %; [P-(MoO3)12] in amount of 6.0-22.0 wt %; active component promoter - nickel oxide NiO, in amount of 3.0-8.0 wt %; carrier modifier - V2O5 in amount of 0.5-5.0 wt % and SnO2 in amount of 0.1-4.0 wt %; aluminium oxide Al2O3 in amount of 84.4-21.0 wt %. Described also is a method of preparing said catalyst, involving saturation of the carrier with a solution of a molybdenum or nickel compound, involving synthesis and saturation of the modified carrier: V2O5, SnCl4·5H2O, H4[Si(W12O40)]·10H2O, H4[P(W12O40)]·10H2O is added to aluminium hydroxide peptised with a monobasic acid; the mixture of starting compounds is evaporated to residual moisture of 60-70%, moulded in form of extruded articles, dried and calcined, with the final calcination temperature of the carrier equal to 550°C; the calcined extruded articles then undergo one-time saturation with an impregnating solution which contains heteropoly-compounds of molybdenum H4[Si(Mo12O40)]·21H2O, H4[P(Mo12O40)]·14H2O and nickel nitrate Ni(NO3)2·6H2O, with pH of the medium equal to 3.0-5.5, followed by thermal treatment of the ready catalyst.

EFFECT: catalyst characterised by high activity when hydrofining heavy petroleum cuts is obtained.

5 cl, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: method of producing nano-sized Pt-Ni catalyst involves preparation of a mixture of starting compounds - carbonaceous material, hexachloroplatinic acid, a nickel salt in a solution containing ethylene glycol, adding to the mixture of starting compounds an alkali solution, reducing Pt and Ni metals, cooling the mixture to room temperature, washing and drying the catalyst. The ethylene glycol solution also contains ethyl alcohol in accordance with 2-3 parts of ethylene glycol and 1-2 parts of ethyl alcohol. Pt and Ni metals are reduced by adding to the solution 1M sodium boron hydride in 1M sodium hydroxide solution for 1-1.5 hours, and the mixture is treated with ultrasound while bubbling inert gas through the mixture. The carbonaceous material used is Vulcan XC-72 soot or nanotubes, or nanofibre. The inert gas used is argon, helium or neon.

EFFECT: shorter time and low power consumption of the process of producing the catalyst.

10 cl, 10 ex

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