Hydrocarbon conversion catalysts and a method for preparation thereof

FIELD: catalyst preparation methods.

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

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

9 cl, 2 dwg, 2 tbl, 6 ex

 

The technical field to which the invention relates.

The invention relates to catalysts for transformations of hydrocarbons and, in particular, relates to catalysts for the conversion of hydrocarbon-based synthetic mesoporous crystalline materials and the method of their derivation. The proposed catalysts can be used in the processes of isomerization of light gasoline fractions, isodewaxing diesel and oil fractions, the alkylation of ISO-alkanes with reaction alkenes, hydrocracking and other processes in oil refining.

The level of technology

Currently, the attention of researchers is focused on the development of catalytic systems on the basis of zirconium oxide modified with anionic additives containing metals of group VIII elements, which exceeds the characteristics of the known catalysts used in various fields of oil refining and petrochemistry.

It is known that the activity of catalysts for conversion of hydrocarbons increases with increasing concentration of active centers. This can be achieved by increasing the specific surface of the catalyst and increasing the availability of active sites of the molecules of the reagent by increasing the pore radius.

Known sulfated zirconium oxide catalyst obtained by conventional method, including Sardinia gel oxide of zirconium salts Zirconia, its impregnation with ammonium sulfate, calcining at 500°and application of metals of group VIII, wet impregnation (V.C.F.Holm, G.C.Bailey, U.S. Patent No. 3032599). The resulting catalyst has a relatively low activity, which is associated with a low specific surface area (˜100 m2/g).

The known method of synthesis of sulfated zirconium oxide catalysts containing metals of group VIII, which is a modification of the traditional method of precipitation-impregnation in the form of replacement of ammonium sulfate sulfuric acid solution while maintaining the remaining stages, which leads to the formation of the catalyst specific surface area of up to 150 m2/g (.Matsuzawa, EP 0925830). The disadvantage of the catalyst obtained by this method is relatively low activity.

There is a method of preparation of the catalyst, including the formation of a gel of zirconium oxide by washing and keeping the reaction mixture in the environment of acetone or methanol, or by joint precipitation of hydrated zirconium oxide and aluminum, subsequent impregnation with ammonium sulfate and the deposition of platinum on the oxide carrier by impregnation on capacity (G.Szabo, P.Nascimento, A.Milan, S.Decker, J.Denayer, J.-P. Dath, U.S. Patent No. 6448198). Specific surface area of the catalysts obtained in this way is 150-160 m2/g, total pore volume is 0.2-0.25 cm3/g with a pore diameter of up to

The known method of synthesis of sulfated zirconium oxide catalyst containing an element of group VIII, based on a Sol-gel method, comprising the synthesis of Sol of zirconium in aqueous ammonia solution in the presence of hydroxypropyl-methyl cellulose and starch, the formation of microspherical or spherical structure of the gel, its gelation, washing and drying, followed by impregnation with an aqueous solution of ammonium sulfate and elements of group VIII and annealing at 450-700° (.Marella, M.Tomaselli, L.Maergalli, F.Pinna, U.S. Patent No. 6180556). Specific surface area of the catalysts obtained in this way, reaches 235 m2/g, total pore volume of 0.17 cm3/g with a pore diameter of 1.4 and 2.3 nm. The disadvantages of the catalysts obtained by the above methods, can be attributed to the low thermal stability due to the inability of the formation of regular broad porous structures with controlled pore.

The closest to the proposed invention is a catalyst based on sulfated ZrO2with mesoporous structure, prepared by two-step method (W.M.H.Sachtler, Y.Y.Huang, U.S. Patent No. 5786294). In the first stage, carry out the hydrothermal crystallization of a mixture of Zr(OPri)4and C16H33NH2in the solution of water-ethanol-acetylacetone, the separation of the solid material by centrifugation and removed the e organic matrix by extraction with ethanol. In the second phase are stabilized aqueous solution of sulfuric acid and calcination, followed by the application of VIII group metals (Pt, Pd, Rh, Ru, Ni). On radiographs of the catalyst is observed reflex corresponding to the interplanar distance in theThe specific surface of the catalyst is 91-347 m2/g and pore volume equal to 0.16-0.31 in cm3/year of the disadvantages of this method include the fact that the obtained catalyst mesoporous structures do not have sufficient stability during heat treatment and the use of expensive and-low-tech source substances (Zr(OPri)4,) and processes (namely the extraction with ethanol, centrifugation).

Disclosure of inventions

The proposed invention aims at creating a catalyst for conversion of hydrocarbons on the basis of mesoporous zirconium oxide containing a metal of group VIII elements, having a high specific surface area (more than 200-300 m2/g) and pore volume (at least) and high thermal stability to withstand repeated cycles of regeneration (for example, removal of coke calcination in air at high temperatures and method of producing the catalyst on the basis of output in industry available large-scale products.

In accordance with this object of the proposed invention is a catalyst for conversion of hydrocarbons having the composition of the metal of group VIII/SO42-/ZrO2-EAxwhere e=the element III or group IV of the periodic table of Mendeleev, x=1.5 or 2, the content of SO42-is 0.1-10 wt.%, the molar ratio of ZrO2:EAx=1:(0.1 to 1.0), and having a mesoporous crystalline structure with a specific surface area of 300-800 m2/g and a total pore volume of 0.3-0.8 cm3/year

Another object of the invention is a method of producing catalyst for conversion of hydrocarbons, including deposition of zirconium compounds under hydrothermal conditions in the presence of a surfactant to obtain mesoporous phase, stabilization stabilizing agent, calcining, and the introduction of a metal of group VIII of the periodic table of Mendeleev, and as compounds of zirconium use of zirconium hydroxide or Zirconia, as a stabilizing agent will use the elements of III or group IV, and after stabilization, if necessary, carry out the regulation of acidity.

Preferably the zirconium hydroxide or Zirconia get a deposition from their respective salts.

In the private embodiment of the invention, the zirconium hydroxide or Zirconia preferably precipitated water is a solution of ammonia.

In another particular embodiment of the invention the precipitation of zirconium hydroxide or Zirconia under hydrothermal conditions is carried out on the composition ZrOa(OH)b-H2SO4-H2O, where a=0-2, b=0-4.

In the particular case of the invention, the metal of group VIII is injected ion exchange or impregnation.

In yet another particular case of the invention, the regulation of acidity carry out the processing of aqueous solutions of acids and/or their salts, as salts are used, for example, ammonium salt.

The preferred mode of calcination of the catalyst is the temperature range 450-900°while retaining its porous characteristics.

Brief description of drawings

Figure 1 presents the x-ray corresponding to the invention, the catalyst for conversion of hydrocarbons on the basis of zirconium oxide, calcined in air at 550°.

Figure 2 presents the distribution of the pore sizes corresponding to the invention, the catalyst based on zirconium oxide, calcined in air at 550°obtained according to the adsorption measurements.

The implementation of the invention

The method of producing the catalyst comprises in the first stage, the preparation of a composition consisting of hydrated zirconium oxide, sulfa the anions and water, by depositing hydrous oxide phases of soluble salts of zirconium or Zirconia with their subsequent dissolution in concentrated sulfuric acid and diluting with water. The resulting composition is subjected to presideny under hydrothermal conditions in the presence of cationic surfactants, used as a matrix, with the formation of the mesoporous structure. In the second phase are stabilized mesoporous structure by treatment with compounds of elements of the III-IV group, taken in a certain relationship to the mesoporous crystalline phase. In the third step, if necessary, produce the regulation of acid-base properties of mesoporous material additional handling acids or their salts, as well as perform the annealing. The fourth stage of the conduct causing the metal of group VIII impregnation or ion exchange.

The preparation of the catalyst corresponding to the proposed invention, carried out by the following method.

In the first stage, a solution of salt of zirconium or Zirconia (ZrOCl2, ZrO(NO3)2) treated with an aqueous solution of ammonia in a molar ratio of 1 Zr : 4NH3. The precipitate is separated, washed with water, and then treated with sulfuric acid in a molar ratio of 1 Zr:(1.5 to 2.5)SO42-to dissolve the precipitate. To the resulting plants is oru add an aqueous solution of a cationic surfactant of the halide of alkyltrimethylammonium ((C n(CH3)3NHal, where n=10-20, Hal=Cl, Br)) in a molar ratio of 1 Zr:(0,2-0,5)n(CH3)3NHal:(400-600)H2O and maintained at a temperature of 40-120°for 20-100 hours. After crystallization of the obtained mesoporous crystalline material based on zirconium oxide containing organic matrix, filtered, washed and dried.

In the second phase are stabilized mesoporous crystalline phase of zirconium oxide. To this mixture, containing the original form of the mesoporous crystalline phase, the composition of R4NOH-SiO2(Al2About3) (where R=Me, Et) and water in a molar ratio of 1 Zr:(0.1 to 1.0):SiO2(Al2About3):(0.1 to 1.0)R4NOH:(100-300)H2O maintained at a temperature of 40-100°for 4-60 hours after crystallization original form mesoporous crystalline phase of zirconium oxide was filtered, washed and dried.

At the third stage, if necessary, the resulting material is treated with an aqueous solution of the acid Hn(For example, sulfuric, wolframtones and others) or their ammonium salts in a molar ratio of 1 ZrO2:(0,01-0,1)Andn. The material is dried and calcined at a temperature of 500-700°C for 4-8 hours.

At the fourth stage, the application of the VIII group metals from aqueous solutions of chloride or ammonium complexes of metals of group VIII ion exchange rate is Mr. or impregnation. The resulting catalyst is dried and calcined at 400°C for 2 hours

The obtained catalyst for conversion of hydrocarbons corresponding to the proposed invention is substantially outweighed by its characteristics known catalysts, and it has a specific surface area of 600-650 m /g and the total pore volume of 0.5-0.6 cm3/year of Chemical composition in a molar ratio equal to 1 ZrO2:(0,1-1,0)SiO2(Ab2About3):(0,01-0,1)SO42-:(of 0.0005-0.05) metal of group VIII. The radiograph of a catalyst characterized by the presence of reflex corresponding to the interplanar distance(Figure 1), which indicates the formation of a structured mesoporous phase. This reflex persists after annealing at 550-600°that proves the safety of mesoporous structure. The average pore diameter of the claimed material is(Figure 2).

Implementation of the proposed method of obtaining a catalyst corresponding to the proposed invention is illustrated by Examples 1-6. Conditions of preparation of the catalyst are summarized in Table 1. Physico-chemical characteristics of the catalysts obtained after calcination in air at 550°prepared in accordance with the proposed method and catalyst known from US Patent 5786294, summarized in T the blitz 2.

The catalysts corresponding to the invention were tested in the reaction of isomerization of linear alkanes With4-C7. Prior to testing, the catalyst restore in a stream of hydrogen at a temperature of 200°C. All catalysts exhibit high activity. In particular, the output of isomers when the conversion of n-butane and n-hexane at 1 ATM exceeds 30% and 70%, respectively.

Table 1.

Conditions of preparation of mesoporous catalysts
ExampleThe original connectionMatri CADeposition conditionsConditions stabilizationRegulation of acidityNonnenmacher
1ZrOCl2CTABr48 h, 95°Zr:Si=1.7, 304, 90°-H2PtCl6
2ZrOCl2CTACl48 h, 95°Zr:Si=1.7, 304, 90°-H2PtCl6
3ZrOCl2CTABr48 h, 95°Zr:Si=1.7, 304, 90°H2SO4 S:Zr =0,08H2PtCl6
4ZrOCl2CTABr48 h, 95°Zr:Si=1.7, 304, 90°(NH4)2SO4, S:Zr=0,08H2PtCl6
5Zr(SO4)2CTABr48 h, 95°Zr:Si=1.7, 304, 90°(NH4)2SO4, S:Zr=0,08H2PtCl6
6ZrOCl2CTABr48 h, 95°Zr:Si=1.7, 304, 90°(NH4)2SO4, S:Zr=0,08H2PdCl4
The known methodZr(OPr)4CNH2120 h, 20°-H2SO4and 0.5 M aq, 15 ml/Gcat10 minPt, Pd
Note: CTABr - bromide of hexadecyltrimethylammonium, CTACl - chloride of hexadecyltrimethylammonium, CNH2- hexadecylamine.
Table 2.

Physico-chemical characterization of mesoporous catalysts after calcination at 550°
Example2/gPore volume, cm3/g
1601±50,68
2550±60,55
3566±50,32
4571±50,63
5599±50,59
6598±50,60
Known215±20,16

Measurement of physico-chemical characteristics of the target products was carried out as follows.

Specific surface area and pore volume were measured on the adsorption porosimetry Micromeritics ASAP 2020 by adsorption of nitrogen. Specific surface area calculated by the BET model (Brunauer-Emmett-Teller) at a relative partial pressure p/P0=0,2. Total pore volume and the pore radii calculated from the adsorption curve using the bjh's model (Barrett-Joyner-Halenda) at a relative partial pressure p/P0=0,99.

R is theogamy samples of catalysts, relevant to the proposed invention, is made on the device X'pert PRO PANAlytical in monochromatization CuKαthe radiation. The calculation of values of interplanar distances d carried out by the formula d=λ/2sinθwhere θ - angle of maximum reflex.

The catalytic activity of the samples was studied in reactions of transformation of linear alkanes C4-C7in running the install with nepodvizhnom layer of the catalyst at pressures of 0.1 to 3.5 MPa and temperatures 160-380°C. the feed Rate is 0.5-2 h-1, the volumetric ratio of hydrogen: raw = 400-1000, the catalytic activity test in 30 min after establishing the desired mode.

Example 1.

The synthesis of the catalyst is carried out in four stages.

At the first stage 10,12 g (0.03 mol) of the chloride Zirconia (ZrOCl2·8H2O) dissolved in 60 g of water. The resulting solution was treated with 4.4 ml of a 25%aqueous solution of NH4IT's up to complete precipitation of the hydrous oxide phases. The precipitate was separated by filtration, washed on the filter with water and then treated 6,16 g (0.06 mol) of concentrated sulfuric acid to dissolve the hydrated oxide phase. To the mixture is added to 37.1 g of water. The resulting solution is added dropwise with vigorous stirring for 30 min, poured to the solution of a surfactant containing 6,13 g (to 0.016 mol) of the bromide hexadecyltrimethyl is monia in 175 g of water. The mixture was kept at a temperature of 95°C for 48 hours. The product is cooled to room temperature, separated by filtration, washed on the filter with water and dried at room temperature for 48 hours

In the second phase are stabilized mesoporous phase. 10 g of dry product obtained in the first stage, suspended in 50 g of water. To the resulting suspension was added with stirring a solution containing at 2.93 g (0.045 mol) of silicon oxide, 32,96 ml of 20%solution (0.045 mol) of hydroxide of tetraethylammonium in water and 15 g of water. The molar ratio of Zr:Si is 1.7. The mixture was kept at a temperature of 90°C for 30 hours. The product is cooled to room temperature, separated by filtration, washed on the filter with water and dried at room temperature for 48 hours

In the third step, the catalyst was calcined at 550°C.

At the fourth stage, the deposition of platinum by the method of circulating impregnation from a solution of hexachloroplatinic acid. 10 g of dry product obtained in the previous step, impregnated with 50 ml of a solution containing 0.05 g of platinum in the form of H2PtCl6. Impregnation can be performed during 1 h at 50°s, then the solution is separated and the catalyst is dried at room temperature for 24 h and at 100°C for 6 hours, the Catalyst was calcined in air flow at 400°C for 3 hours

the example 2.

Synthesis is carried out as in Example 1. At the first stage as a surfactant, a mixture of 21,55 ml of 25%aqueous solution of chloride of hexadecyltrimethylammonium 159 ml of water.

Example 3.

The synthesis of the catalyst is carried out in four stages. The first, second and fourth stages are carried out as in Example 1.

In the third stage before the calcination is conducted additionally, the regulation of the acid properties. 10 g of dry product obtained in the second step, is treated with a solution of 0.5 g (0,005 mol) of sulfuric acid in 50 g of water. The mixture was kept at room temperature for 1 h, then evaporated and dried at 100°C for 2 hours the Product is calcined in air flow at a temperature of 550°C for 6 hours

Example 4.

Synthesis is carried out according to Example 3. In the second stage, the molar ratio of Zr:Si is 1.7. The stabilization time of 30 hours. Regulation of acidity in the third stage is conducted with a solution of 0.66 g (0,005 mol) of ammonium sulfate in 50 g of water.

Example 5.

Synthesis is carried out according to Example 3, except that at the first stage as the initial connection charge sulfate zirconium.

In the first stage, 15 g (0,042 mol) Zr(SO4)2·4H2O dissolved in 50 g of water. The resulting solution is added dropwise with vigorous stirring for 30 min, poured to a solution 8,24 g (0,021 mol) of bromide of hexadecyltrimethylammonium in 235 g of water. The mixture is maintained at a rate which the atur 95° With in 48 hours. The product is cooled to room temperature, separated by filtration, washed on the filter with water and dried at room temperature for 48 hours

The second, third and fourth steps performed according to Example 3.

Example 6.

The first, second and third stages are carried out according to Example 3. In the fourth stage, carry out the application of palladium from a solution paradichlorobenzene acid. 10 g of dry product obtained in the third stage, soaked in 50 ml of a solution containing 0.05 g of Pd in the form of H2PtCl4. Impregnation can be performed during 1 h at 50°C. the Solution is separated and the catalyst is dried at room temperature for 24 h and at 100°C for 6 hours, the Catalyst was calcined in air flow at 400°C for 3 hours

Industrial applicability

The catalysts corresponding to the proposed invention, are of great interest for use in the processes of isomerization of light gasoline fractions, isodewaxing diesel and oil fractions, the alkylation of ISO-alkanes with reaction alkenes, hydrocracking and other Interest determined by high thermal stability and additional features due to the peculiarities of the crystal structure, combining a wide pores (over), uniform in size, large values of specific surface area and pore volume as well as the possibility of the formation of specific active sites on the internal surface of the pores.

1. The catalyst for conversion of hydrocarbons having the composition of the metal of group VIII/SO42-/ZrO2-EAxwhere e=the element III or group IV of the Periodic table of Mendeleev, x=1.5 or 2, the content of SO42-is 0.1-10 wt.%, the molar ratio of ZrO2:EAx=1:(0.1 to 1.0), and having a mesoporous crystalline structure with a specific surface area of 300-800 m2/g and a total pore volume of 0.3-0.8 cm3/year

2. The method of producing catalyst for conversion of hydrocarbons, including deposition of zirconium compounds under hydrothermal conditions in the presence of a surfactant to obtain mesoporous phase, stabilization stabilizing agent, calcining, and the introduction of a metal of group VIII of the Periodic table of Mendeleev, characterized in that compounds of zirconium use of zirconium hydroxide or Zirconia, as a stabilizing agent will use the elements of III or group IV, and after stabilization, if necessary, carry out the regulation of acidity.

3. The method according to claim 2, characterized in that the zirconium hydroxide or Zirconia get a deposition from their respective salts.

4. The method according to claim 3, characterized in that the zirconium hydroxide or Zirconia precipitated with an aqueous solution of ammonia.

5. The method according to claim 2, characterized in that the precipitation of the hydroxide zirconyl of Zirconia under hydrothermal conditions is carried out song ZraOb(OH)c-H2SO4-H2O.

6. The method according to claim 2, characterized in that the introduction of a metal of group VIII carry out ion exchange or impregnation.

7. The method according to claim 2, characterized in that the regulation of acidity carried out with aqueous solutions of acids and/or their salts.

8. The method according to claim 7, characterized in that the salts used ammonium salt.

9. The method according to claim 2, characterized in that the annealing is carried out at temperatures 450-900°C.



 

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13 cl, 1 tbl, 24 ex

FIELD: exhaust gas neutralization catalysts.

SUBSTANCE: catalyst contains at least one zeolite and additionally at least one oxide carrier selected from alumina, silica, titanium dioxide, and aluminum silicate, and also at least one precious metal selected from platinum, palladium, rhodium, and iridium. The latter are characterized by average oxidation degree below +2.5, average number of metal ligands more than 3, and average number of oxygen ligands less than 3, whereas precious metal atoms are present on zeolites and oxide carriers in the form of crystallites with average particle size 1-6 nm. Catalyst is prepared on an solid cellular element, for which oxide carriers and zeolites are first separately impregnated with precious metal precursors and then calcined in yet wet state by blowing them into gaseous combustion gases at 500-1000°C for 0.1 to 10 sec. Thereafter, common coating dispersion is processed, which is further used to coat solid cellular element. Coating is then dried, calcined, and reduced.

EFFECT: increased catalytic activity, prolonged lifetime of catalyst, and lowered minimum working temperature at which carbon monoxide and hydrocarbons start being catalytically converted.

10 cl, 8 tbl, 11 ex

FIELD: alternative fuel production and catalysts.

SUBSTANCE: invention relates to (i) generation of synthesis gas useful in large-scale chemical processes via catalytic conversion of hydrocarbons in presence of oxygen-containing components and to (ii) catalysts used in this process. Catalyst represents composite including mixed oxide, simple oxide, transition element and/or precious element, carrier composed of alumina-based ceramic matrix, and a material consisting of coarse particles or aggregates of particles dispersed throughout the matrix. Catalyst has system of parallel and/or crossing channels. Catalyst preparation method and synthesis gas generation method utilizing indicated catalyst are as well described.

EFFECT: enabled preparation of cellular-structure catalyst with high specific surface area, which is effective at small contact times in reaction of selective catalytic oxidation of hydrocarbons.

6 cl, 2 tbl, 16 ex

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