Catalyst for aromatization of alkanes, method of preparation thereof, and aromatization of hydrocarbons using the same

FIELD: organic synthesis catalysts.

SUBSTANCE: invention relates to catalyst for aromatization of alkanes, to a method of preparation thereof, and to aromatization of alkanes having from two to six carbon atoms in the molecule. Hydrocarbon aromatization method consists in that (a) C2-C6-alkane is brought into contact with at least one catalyst containing platinum supported by aluminum/silicon/germanium zeolite; and (b) aromatization product is isolated. Synthesis of above catalyst comprises following steps: (a) providing aluminum/silicon/germanium zeolite; (b) depositing platinum onto zeolite; (c) calcining zeolite. Hydrocarbon aromatization catalyst contains microporous aluminum/silicon/germanium zeolite and platinum deposited thereon. Invention further describes a method for preliminary treatment of hydrocarbon aromatization catalyst comprising following steps: (a) providing aluminum/silicon/germanium zeolite whereon platinum is deposited; (b) treating zeolite with hydrogen; (c) treating zeolite with sulfur compound; and (d) retreating zeolite with hydrogen.

EFFECT: increased and stabilized catalyst activity.

26 cl, 1 dwg, 5 tbl, 4 cl

 

The technical field to which the invention relates.

The present invention relates to a catalyst for aromatization of alkanes to aromatic hydrocarbons, specifically to the zeolite, preferably with structure type MFI, most preferably the ZSM-5 MFI, the catalyst for aromatization of alkanes having two to six carbon atoms in the molecule, aromatic hydrocarbons such as benzene, toluene and xylene.

The level of technology

Zeolite is a crystalline hydrated aluminosilicate, which may also contain other metals, such as sodium, calcium, barium and potassium, and which has ion-exchange properties (Encarta@ World English Dictionary [North American Edition] © & (P) 2001 Microsoft Corporation). The method of producing zeolite includes: (a) preparation of an aqueous mixture of silicon dioxide and aluminum oxide; and b) maintaining the specified water mixture at crystallization conditions, until, until crystals are formed of the specified form of the zeolite. Most studies of zeolites has been devoted to the synthesis of zeolite frameworks containing elements other than silicon and aluminum.

In U.S. patent No. 6160191 described that the term "zeolite" includes not only the silicates, but also compounds in which the aluminum is replaced by gallium, titanium, iron or boron, and compounds in which the silicon semesterbased, tin and phosphorus. In U.S. patent No. 3329480 and 3329481, which are both issued D.A.Young, reported the existence of crystalline zirconosilicate and titanosilicate zeolites. The zeolite containing chromium in tetrahedral positions described Ermolenko, etc. in Proceedings of the second all-Union conference on zeolites, Leningrad, 1964, s-178 (published in 1965). However D.W.Breck in the book (Zeolite molecular sieves) Zeolite Molecular Sieves, S. 322, John Wiley & Sons (1974), suggested that the existing chrome is not contained in the structure of zeolite a and, moreover, that chromium is present in undissolved form, as an admixture. Suggested that this admixture is in the form of chromium silicate, which is confirmed by the nature of the adsorption isotherms of water vapor.

Zeolite ZSM-5 was synthesized with many different aluminum elements in the frame, including iron. Synthesis of iron containing zeolite structure described in the document of Japanese Kokai 59121115, published July 13, 1984, which revealed the aluminosilicate having the structure faujasite and containing coordinated iron. It is noted that the chemical composition corresponds to the formula s2/nAbout:bFe2O3:Al2O3:cSiO2in which M can mean H, alkali metal or alkaline earth metal; the symbol n represents the valency of M; a=1±0,3; value is between 4.6 and 100; and a is less the, than b, where a and b is less than 7. The lattice parameter and0is between a 24.3 and 24.7 angstroms. Similarly, in U.S. patent No. 4208305 disclosed crystalline silicates, which are structurally represent a three-dimensional framework of tetrahedra SiO42-, FeO42-that may not AlO42-, GaO42-and GeO42-that are linked by common oxygen atoms and digidratirovannogo are of the total composition:

(1,0±0,3) (R)2/nO [aFe2O3:bAl2O3:cGa2O3] y(dSiO2eGeO2),

where R represents a cation; and≥0,1; b≥0;≥0, a+b+c=1; y≥10; d≥0,1; e≥0; the sum of d+e=1, and n denotes the valence of the cation R. silicates are Preferred, not containing gallium, germanium and aluminum. Silicates with a specific x-ray powder diffraction pattern are also preferred.

In U.S. patent No. 4713227 disclosed crystalline metalloaluminophosphates, having a microporous structure, catalytic activity and ion-exchange properties and which contain metals such as arsenic, bismuth, cobalt, iron, germanium, manganese, vanadium and antimony, inside the frame.

In U.S. patent No. 5179054 noted that, although the matrix material can be formed with germanium as analogous to silicon, such the materials are expensive and usually do not exceed metroselect, that is, the aluminosilicate, gallosilikata, ferrosilicate and borosilicate, as the molecular sieve component of the catalyst for catalytic cracking of heavy hydrocarbon fractions with the aim of obtaining hydrocarbons boiling in the range of gasoline and other distillates.

In the publication "Aromatization of Bhutan on intermetallic Pt-Ge compounds deposited on HZSM-5", T. Komatsu, and others, in the journal Applied Catalysis A: General, C-195, s-339 (2000), as catalysts for the conversion of butane in aromatic hydrocarbons were used intermetallic platinocyanide particles, particles of platinum and germanium deposited on HZSM-5. It is known that the intermetallic catalyst Pt-Ge has a high stability during operation in the process of conversion and high selectivity in comparison with platinum catalyst. It is noted that for a catalyst with a large ratio of germanium to platinum observed reduced degree of conversion of butane and reduced selectivity for aromatic hydrocarbons.

In U.S. patent No. 4704494 discovered a way of turning low-molecular paraffin hydrocarbons into aromatic hydrocarbons using the modified platinum or gallium metallodielectric (Si/M) catalysts, in which M represents aluminum, gallium, titanium, zirconium, germanium, lanthanum, mA is the Ganz, chromium, scandium, vanadium, iron, tungsten, molybdenum, Nickel, or their mixture. In the working examples were obtained catalysts in which the metal M represents aluminum or gallium. Examples for Germany were not represented. There are no assumptions about the choice of Germany from any other elements or mixtures of elements.

In U.S. patent No. 5456822 described by way of aromatization of hydrocarbons containing from two to nine carbon atoms in the molecule, using a catalyst consisting of a zeolite of MFI, the skeleton of which are silicon, aluminum and/or gallium, matrix, and gallium, a noble metal from the family of platinum and a metal selected from tin, germanium, indium, copper, iron, molybdenum, gallium, thallium, gold, silver, ruthenium, chromium, tungsten and lead deposited on the zeolite. Examples for Germany were not represented. There are no assumptions about the choice of Germany from any other elements or mixtures of elements.

In U.S. patent No. 4910357 and 5124497 describes a method for monosubstituted monoalkylamines hydrocarbons from paraffins C8+using non-acidic platinum source of catalyst, in which the crystalline material contains tin, indium, thallium, or lead. These catalysts had a much greater selectivity for aromatic hydrocarbons, other than latinova catalysts, containing other elements in the crystalline material including germanium.

In U.S. patent No. 6315892 disclosed a method of producing the catalyst from the carrier, platinum, and Germany, in which germanium is introduced in the form of organic compounds, which is in contact with the catalyst precursor in the reaction zone.

In U.S. patent No. 5227557 described by way of aromatization of hydrocarbons containing 2 to 4 carbon atoms in the molecule, using MFI zeolite catalyst containing platinum and another metal selected from tin, germanium, lead and indium. As platinum, and an additional metal can be introduced into the MFI zeolite by impregnation, exchange or other known methods. In the working examples of the method of impregnation as for platinum, and the additional metal. Catalyst F contained 0.3% of platinum and 0.2% Germany.

In U.S. patent No. 4036741 disclosed a method of converting hydrocarbons (including dehydrocyclization paraffins to aromatic hydrocarbons) on the acid catalyst from porous media containing halogen, along with platinum, cobalt, and germanium, which are evenly dispersed throughout the material of the carrier, which may be a crystalline zeolite aluminosilicate. This catalyst was tested as a catalyst for reforming of gasoline f the shares with a relatively low octane number, in the conditions of absence of sulfur, in comparison with a catalyst containing platinum and germanium, but without cobalt. From these results it follows that the cobalt is an essential additive for improving the activity and stability of catalyst activity.

Some zeolite catalysts containing a metal of group VIII, are sensitive to sulfur poisoning. For some platinum catalysts, despite some sensitivity to sulfur, moderate sulfur content, such as from 10 to 100 ppm is acceptable and sometimes preferred. The standard method of acarnania, which is well known in the prior art is that the catalyst is heated in the presence of hydrogen sulfide or a mixture of hydrogen sulfide and hydrogen or nitrogen to a temperature of between 150 and 800°C, preferably between 250 and 600°C.

It would be desirable to develop a zeolite catalyst of the type that maintains a relatively constant selectivity in the conversion of lower alkanes to aromatic hydrocarbons such as benzene, toluene and xylene during the period of their operation.

Tasks inventions

Accordingly, an objective of this invention to provide an aluminum-silicon-germanium zeolite on which the deposited platinum, with the specified catalyst has a relatively constant selectivity is when converting lower alkanes to aromatic hydrocarbons.

Another objective of this invention is to develop a method of producing catalyst - aluminum-silicon-germanium zeolite on which the deposited platinum.

In addition, the task of this invention is to develop a way of aromatization of hydrocarbons using a catalyst - aluminum-silicon-germanium zeolite on which the deposited platinum.

In addition, the task of this invention is to develop a method for pretreatment of the catalyst for the aromatization of hydrocarbons - aluminum-silicon-germanium zeolite on which the deposited platinum.

The invention

Objectives of the invention are performed using a microporous aluminum-silicon-germanium zeolite on which the deposited platinum. This catalyst synthesized by obtaining a zeolite containing aluminum, silicon and germanium in the cage, the deposition of platinum on the zeolite and calcining the zeolite. The zeolite may have a structure MFI, FAU, TON, MFL, VPI, MEL, AEL, AFI, MWW or MOR, but preferably, the zeolite has an MFI structure, more preferably it is an MFI zeolite ZSM-5. The catalyst used in the process of aromatization of alkanes by contacting at least one alkane with a microporous aluminum-silicon-germanium zeolite on which the deposited platinum, in terms of flavoring with the release of the product and is omatsola.

Brief description of drawing

A more complete recognition of this invention and many of its attendant advantages may be readily attained by reference to the following detailed description, when taken up in connection with the attached drawing.

The drawing shows a graphical change in the degree of conversion (%) or selectivity of the catalyst of the present invention in the operating time in hours.

Detailed description of the invention

It was found that the deposition of platinum on the zeolite catalyst precursor MFI, aluminosilicate framework which introduced germanium, get the catalyst, which has a high stability in time of the operation, i.e. it maintains a relatively constant selectivity in the conversion of lower alkanes to aromatic hydrocarbons, for example alkanes containing from two to six carbon atoms in the molecule, benzene, toluene and xylene.

This zeolite can be obtained by any known method of obtaining MFI structure of aluminum, silicon and germanium. It is known that zeolites are crystalline silicates and include patterns tetrahedra4that form a three-dimensional grid by linking through shared oxygen atoms, where T represents tetravalent silicon and trivalent aluminum. This aluminum may be amesen trivalent elements, such as gallium, and much less boron or beryllium.

Typically, zeolites crystallize from aqueous solution. A typical method for the synthesis of zeolites is the transformation of amorphous gel in zeolite crystals in hydrothermal process using the mechanism of dissolution/recrystallization. In addition, the reaction medium contains structuring agents, which are introduced into the microporous space mesh zeolite during crystallization, and thus, is governed by the mesh design and facilitated the stabilization of the structure due to interaction with components of the zeolite.

As disclosed in U.S. patent No. 5246688, which is included in the description as the link, zeolites MFI-based silicon oxide, and optionally, oxides of titanium, germanium, zirconium and/or tin, are obtained by: 1) heating the aqueous homogeneous reaction mixture, which includes: a) complex M2/nSiF6in which M represents a cation with a valency of n, and optionally at least one set of M2/nT′F6in which T′ represents titanium, zirconium, germanium and/or tin, b) a reagent that provides ions of HE-due to the hydrothermal decomposition and structuring agent, e.g. a tertiary amine or a compound of Quaternary ammonium, resulting in a mixture of obrazets the sediment zeolite, and 2) separation and ignition of the specified sediment, in order to remove the structuring agent from the pores and channels of the obtained zeolite.

In addition, methods for producing zeolite MFI can be found in U.S. patent No. 3702886 and log J.Phys. Chem., Tom, s-5684 (1993), which is included in the description as a reference.

The atomic ratio of silicon/germanium to aluminum (Si-Ge:Al) in the MFI zeolite is preferably greater than 25:1, more preferably is in the range of from 45:1 to 250:1, and most preferably from 50:1 to 100:1. The ratio of silicon oxide to germanium dioxide is in the range from 100:1 to 8:1, more preferably in the range from 50:1 to 10:1, and most preferably from 25:1 to 11:1.

Platinum is deposited on the zeolite MFI by any known method of deposition of metal on the zeolite. Typical methods of deposition of metal on the zeolite is ion exchange and impregnation. Preferably, platinum is present in the range from 0.05% to 3%, more preferably in the range from 0.2% to 2%, and most preferably in the range from 0.2% to 1.5%.

The catalyst may be associated with oxides of magnesium, aluminum, titanium, zirconium, thorium, silicon, boron and mixtures thereof. Preferably, the carrier is amorphous and is an aluminum oxide.

Preferably, the catalyst has an average pore size in the preferred range of sizes from 5 to 100 angstroms, more before occhialino in the range of from 5 to 50 angstroms, and most preferably in the range of sizes of micropores from 5 to 20 angstroms.

The catalyst may contain a reaction product, such as platinum sulfide, which is formed when the contact element or compound deposited on the surface of the catalyst with the sulfur compound. Non-limiting examples of sulfur compounds are H2S, CnH2n+2S, where n=1-20, CnH2n+1S2where n=2-22 and CnH2n+1S, n=2-22. The sulfur compound may be added before or in the process of aromatization of light alkanes, that is, the catalyst may be pretreated with sulfur or the sulfur compound may be introduced together with hydrocarbons when it is in contact with the catalyst during the process of aromatization. The amount of sulfur in the catalyst is preferably in the range from 10 to 0.1 wt.%.

The chemical formula of the catalyst may be represented as:

M[(SiO2)(XO2)x(YO2)y]Z+y/n

where M is a noble metal such as platinum or gold, X represents titanium, germanium, tin, or another tetravalent element, Y represents boron, aluminum, gallium, indium, tellurium, or another trivalent element, Z is a cation with valence n, such as N+, Na+To+, Rb+Cs+Ca2+2+, Sr2+or VA2+x varies from 0 to 0.15 and y varies from 0 to 0,125. In accordance with the recommendations of the IUPAC example, the catalyst may be represented as:

[H*Pt][Si91Ge4AlO192]-MFI

Since this invention is generally already described, the following examples are given as particular embodiments of the invention and to demonstrate the practical embodiment and advantages of the invention. Understood that these examples are given for purpose of illustration, and they are in no way intended to limit the description or claims.

Example 1

Synthesis of zeolite

Within 20 minutes mix of 40.6 g of colloidal silica (40% SiO2), 2,251 g of aluminium nitrate Al(NO3)3*N2O 19,575 g tetrapropylammonium (HERBS), of 14.7 g of hydrogen fluoride (aqueous solution, 40%) and 91.3 g of methylamine (aqueous solution, 40%) and 39,54 g of water. In this mixture with stirring, added dropwise 3,93 g tetrachloride Germany. Bring the pH value of the mixture to approximately 10 by adding hydrogen fluoride (aqueous solution, 40%). The mixture is stirred for 5 minutes. In the autoclave reactor is transferred 175 g of the mixture and heated at a temperature of 170°C for 18 hours. The resulting solid is washed and dried at a temperature of 90°C overnight and then calcined by load, is of from room temperature to 550° At the rate of 1K per minute, and maintained at a temperature of 550°C for 5 hours. The amount of the obtained product is 13.6,

Molding

Combine 10.4 g of the synthesized above zeolite with 14.9 g of hydrated aluminum oxide, and the mixture is stirred. The mixture is moistened 0,05 N. nitric acid to obtain a pasty mass which mix for 15 hours. This mass is dried overnight at a temperature of 90°and then calcined at 550°C for 5 hours. The obtained solid is pulverized and sieved to obtain a powder 20/40 mesh. (sitonomy the U.S. standard).

The sifted powder with the above stage unite with approximately 125 ml of 1.0-molar solution of ammonium nitrate. Bring the pH value of the mixture to 6 by the addition of 0.05 N. nitric acid. The resulting mixture is placed in a drying Cabinet at a temperature of 60°1 h, with periodic rotation of the mixture. The mixture is decanted and the resulting solid is washed for 30 minutes five aliquot (60 ml) of distilled water at a temperature of 60°C. This solid is optionally dried overnight at a temperature of 90°C.

Ion exchange with platinum

Dissolve in 100 ml of distilled water was 1.94 g (NH3)4Pt(BUT3)2. Unite 33 ml of this solution with 3 g obtained above, CEO the ITA. Bring the pH value of the mixture to 6, adding 0,05 N. nitric acid. This mixture is placed in a drying Cabinet at a temperature of 60°24 hour rotation of the mixture every hour for the first 4 hours the Mixture is decanted and twice repeat the preceding operation. The solid is washed 5 times (each time in a 60 ml) of distilled water at room temperature. The solid is dried overnight at a temperature of 90°and calcined by heating from room temperature to 300°at the rate of 1K per minute, and maintained at a temperature of 300°C for 4 hours.

Pre-treatment with hydrogen sulfide

In the reactor, heated to a temperature of 400°download 4,003 g formed above catalyst and rinsed for 4 hours with a mixture of 50% hydrogen in nitrogen. Flow 50% of the hydrogen is replaced by 1% of hydrogen sulfide (20 ml/min) at 400°until you found the breakthrough of hydrogen sulfide. The stream of hydrogen sulfide is substituted for 50% hydrogen in nitrogen (40 ml/min), and the processing is continued for 1 hour at 400°C.

Comparative example a

The zeolite containing as elements of the frame only silicon dioxide and aluminum oxide and having a ratio of silica/alumina 150/1 (ZEOLYST CBV 15014G), is formed, is subjected to ion exchange, calcined and pre-treated as in the synthesis of zeolite formation and ion exchange rate is not in the preceding example 1.

Comparative example B

Zeolite ZSM-5 (15 g)containing as elements of the frame only silicon dioxide and aluminum oxide (150/1), mixed with fine powder of germanium dioxide (0,30 g). Then this mixture is formed, is subjected to ion exchange, calcined and pre-treated as in the synthesis of zeolite formation and ion exchange in the preceding example 1.

Comparative example

Zeolite ZSM-5 (15 g)containing as elements of the frame only silicon dioxide and aluminum oxide (150/1), mixed with fine powder of germanium dioxide (0.9 g). Then this mixture is formed, is subjected to ion exchange, calcined and pre-treated as in the synthesis of zeolite formation and ion exchange in the preceding example 1.

The test catalysts

The catalysts of experience in stainless steel tubing, using as raw material a mixture of 105 kPa (15 abs. pound/square inch) propane, diluted with nitrogen to a total pressure of 176 kPa (25 abs. pound/square inch). The feed rate of the mass of raw material (SPMS) varies from 0.35 to 1.7 h-1depending on the activity of the used catalyst. Products analyze, continuously taking samples into the gas chromatograph, in which quantified all of the hydrocarbon components containing from 1 to 12 carbon atoms. Selectivity is expressed is raised relative to the weight of the transformed propane, A9+ means aromatic hydrocarbons With9-C11; BTK means benzene+toluene+xylene.

The catalyst of example 1 was tested by aromatization of propane, and the results are shown in table 1. Selectivity for BTK over 100 hours of testing remained constant.

Table 1
The catalyst of example 1, SPS=0,35 h-1the reaction temperature 475°
Time, hConversion, %Methane, wt.%Ethan, wt.%Bhutan, wt.%A9+, wt.%BTK, wt.%
3,53722411656
12,53422413556
24,53322413456
36,53222414456
48,53322414456
of 60.533224143 56
72,53222414356
84,53122414356
96,53122414356
1123022414356
1373222314357
1463122315356

The catalyst of comparative example a was tested in the aromatization of propane, and the results are shown in table 2. Selectivity for BTK during the first 100 hours of the test does not remain constant.

Table 2
The catalyst according to comparative example A, SPMS=0,35 h-1the reaction temperature 465°
TimeConversion, %Methane, wt.%Ethan, wt.%Bhutan, wt.%A9+, wt.%BTK, wt.%
3,5 3922312854
12,53522615650
233723015646
353823216543
473723317641
593523417540
713723518538
833723618538
953623618537
1073523619536
1193423619536
1313323619536/td>
1463323719536

The catalyst of comparative example B was tested by aromatization of propane, and the results are shown in table 3. Selectivity for BTK does not remain constant.

Table 3
The catalyst of comparative example B, SPMS=0,6 h-1the reaction temperature 450°
Time, hConversion, %Methane, wt.%Ethan, wt.%Bhutan, wt.%A9+, wt.%BTK, wt.%
23723012649
2,753923112649
3,53823112648
4,253923212547
53823212547
9,540234 12545
15,53923513544
203823513543
24,53823613543
30,53723613542
353823613542
39,53723613542
45,53723713542
473723613542

The catalyst according to comparative example was tested with the aromatization of propane, and the results are shown in table 4. Selectivity for BTK does not remain constant.

Table 4
The catalyst according to comparative example, SPMS=0,3 h-1temperature re the functions 450°
Time, hConversion, %Methane, wt.%Ethan, wt.%Bhutan, wt.%A9+, wt.%BTK, wt.%
3,2464429045
5,24644310043
9,84544410042
15,23534115041
19,83534115041
25,23434115040
30,53434215040
39,83434115040
49,23434215040
to 75.23334215040
99,23334215040
for 125.83234215039
149,23134215039
175,83134215040
199,23134215039
249,22934116039
292,52834116039

From the above data it can be concluded that while the degree of transformation of raw materials (in percent) for all catalysts was comparable, the catalyst containing aluminum-silicon-germanium zeolite on which was deposited platinum (example 1) had a high selectivity for benzene, toluene and xylene (BTX), which remained constant for 100 hours. Catalysts, zeolite skeleton lacking germanium, over time, lose efficiency (selectivity for BTK).

In rent anowski the diffraction pattern of the powder, below for catalyst according to the present invention was observed following the intensity of the peaks, which were identified according to standard methods (radiation: Cu-K(alpha), the wavelength of 1.54 angstroms).

Table 5
The intensity peaks of the main peaks in the x-ray powder diffraction pattern Ge-ZSM-5
The parameter d, AIntensity
of 11.1540
10,0433
9,7712
6,3813
4,2719
3,85100
of 3.7722
3,7242
3,6635

Given the intensity values calculated in conventional units, taking the intensity of the largest peak for 100. Peaks for Ge-ZSM-5 are shifted towards higher values of the parameter d, compared with zeolite Al-ZSM-5.

In light of the above recommendations, there are numerous modifications and alterations. It should be understood that within the below claims this invention may be practiced otherwise than specifically described above.

1. The way of aromatization of hydrocarbons, which consists in the fact that it contains the following stages:

a) contacting alkane containing from 2 to 6 carbon atoms in the molecule, at least one catalyst containing aluminum-silicon-germanium zeolite on which the deposited platinum; and

b) allocate the product flavoring.

2. The method according to claim 1, in which the contact between alkanol and catalyst occurs at a feed rate in the range between 0.1 and 100 h-1.

3. The method according to claim 1, in which the contact between alkanol and catalyst occurs at a temperature in the range between 200 and 600°C.

4. The method according to claim 1, in which the contact between alkanol and catalyst occurs at a pressure in the range between 35 and 1505 kPa (5-215 abston/square inch).

5. The method according to claim 1, wherein the zeolite has an MFI structure.

6. The method according to claim 1, wherein the catalyst further comprises sulfur.

7. The method according to claim 1, in which the alkane further comprises sulfur.

8. The method of synthesis of aluminum-silicon-germanium-platinum-zeolite catalyst, namely, that contains the following stages:

a) get a zeolite containing aluminum, silicon and germanium;

b) precipitated platinum on the zeolite; and

C) calcined zeolite.

9. The method according to claim 8, in which the platinum is precipitated by cation exchange.

10. The method of claim 8, the platinum which beset by impregnation.

11. The method according to claim 8, in which the zeolite has an MFI structure.

12. The method of claim 8 in which the catalyst is sequentially treated first with hydrogen, then the sulfur compound and then with hydrogen.

13. Aluminum-silicon-germanium-platinum-zeolite catalyst for the aromatization of hydrocarbons containing

(a) a microporous aluminum-silicon-germanium zeolite; and

b) platinum, deposited on a microporous aluminum-silicon-germanium zeolite.

14. The catalyst according to item 13, in which the zeolite has an MFI structure

15. The catalyst according to item 13, in which the catalyst further comprises a sulfur compound.

16. The catalyst according to item 15, in which the sulfur compound is H2S, CnH2n+2S, where n=1-20, WithnH2n+1S2where n=2-22 and CnH2n+1S, n=2-22.

17. The catalyst according to item 13, in which the formula of the catalyst are presented in the form M[(SiO2)(XO2)·(YO2)y]Z+y/nwhere M is a noble metal, X is a tetravalent element, Y represents a trivalent element, Z is a cation with valence n, x varies from 0 to 0.15 and y varies from About to 0,125.

18. The catalyst 17, in which M is platinum.

19. The catalyst 17 in which X represents germanium.

20. The catalyst 17 in which Y means al is mine.

21. The catalyst 17, in which Z represents H+, Na+, K+, Rb+Cs+Ca2+, Mg2+, Sr2+or VA2+.

22. The catalyst according to item 13, in which the catalyst has the formula [H+Pt][Si91Ge4AlO)192]-MFI.

23. The catalyst according to item 13, in which x-ray powder diffraction pattern includes size of peaks, characterized by the parameters d And size: 11,15; 10,04; 9,77; 6,38; 4,27; 3,85; 3,77; 3,72; 3,66 and the intensity values in the amount of: 40, 33, 12, 13, 19, 100, 22, 42, 35.

24. The method of pre-processing catalyst for aromatization of hydrocarbons, which consists in the fact that it contains the following stages:

a) choose the aluminum-silicon-germanium zeolite on which the deposited platinum;

b) the zeolite is treated with hydrogen;

C) the zeolite is treated with a sulfur compound; and

g) zeolite second time is treated with hydrogen.

25. The method according to paragraph 24, in which the zeolite is associated with amorphous aluminum oxide to the first processing stage.

26. The method according to paragraph 24, in which the sulfur compound is H2S, CnH2n+2S, where n=1-20, CnH2n+1S2where n=2-22 or CnH2n+1S, n=2-22.



 

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The invention relates to a method of separation of aromatic hydrocarbons from coke oven gas

FIELD: petroleum processing.

SUBSTANCE: invention, in particular, relates to petroleum fraction hydrofining process utilizing presulfided catalysts. Hydrofining process is described involving contacting petroleum fractions with presulfided catalyst containing alumina-carried cobalt, molybdenum, phosphorus, and boron, said process being conducted at 320-340°C, pressure 3.0-5.0 MPa, volumetric feed supply rate 1.0-6.0 h-1, normalized volumetric hydrogen-containing gas-to-feed ratio (500-1000):1 in presence of catalyst sulfided outside of reactor. Sulfidizing of catalyst is accomplished with hydrogen sulfide at 80-500°C and volumetric hydrogen sulfide flow rate 0.02-6.0 h-1. Chemical composition of catalyst is the following, wt %: MoS2 8.0-17.0, Co3S2 1.5-4.0, P2O3 2.5-5.0, B2O3 0.3-1.0, La2O3 1.0-5.0, and aluminum oxide - the balance.

EFFECT: simplified process.

2 cl, 1 tbl, 3 ex

FIELD: petroleum processing.

SUBSTANCE: invention concerns development of catalysts for use in petroleum fraction hydrofining processes. Presulfidized catalyst including alumina-supported cobalt, molybdenum, phosphorus, and boron, active components of which are converted into operational sulfide form using sulfidizing agent, in particular hydrogen sulfide, at sulfidizing temperature 80 to 500°C and hydrogen sulfide volume flow rate 0.02 to 6.00 h-1, catalyst further contains lanthanum oxide. Composition of catalyst is the following, wt %: MoS2 8.0-17.0, Co3S2 1.5-4.0, P2O5 2.5-5.0, B2O3 0.3-1.0, La2O3 1.0-5.0, and alumina - the balance.

EFFECT: simplified catalyst preparation technology without losses in catalytic and mechanical properties.

1 tbl, 3 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic system of hydrocarbon feedstock hydrofining is activated by circulating hydrogen-containing gas or mixture thereof with starting feedstock through layer-by-layer loaded catalysts in presulfided or in presulfided and oxide form at elevated temperature and pressure. Hydrogen is injected into circulating hydrogen-containing gas or mixture thereof with starting feedstock portionwise, starting concentration of hydrogen in circulating hydrogen-containing gas not exceeding 50 vol %. Starting feedstock consumption is effected stepwise: from no more than 40% of the working temperature to completely moistening catalytic system and then gradually raising feedstock consumption to working value at a hourly rate of 15-20% of the working value. Simultaneously, process temperature is raised gradually from ambient value to 300-340°C. Circulating factor of hydrogen-containing gas achieves 200-600 nm3/m3. Addition of each portion of hydrogen is performed after concentration of hydrogen in circulating hydrogen-containing gas drops to level of 2-10 vol % and circulation of hydrogen-containing gas through catalysts loaded into reactor begins at ambient temperature and further temperature is stepwise raised. Starting feedstock, which is straight-run gasoline or middle distillate fractions, begins being fed onto catalytic system at 80-120°C.

EFFECT: enabled prevention and/or suppression of overheating in catalyst bed.

5 cl, 6 tbl, 12 ex

FIELD: petroleum processing and petrochemistry.

SUBSTANCE: catalytic reforming carried out at temperature in the reforming zone entry not higher than 485°C is supplemented by sulfidizing accomplished by introducing sulfur-containing compounds by doses each constituting 0.001-0.02% sulfur of the weight of catalyst, intervals between doses being not less than 1/2 one dose introduction time and at summary amounts of added sulfur 0.02-0.2% sulfur of the weight of catalyst during additional sulfidizing period. Additional sulfidizing is performed one or several times over the service cycle lasting hundreds or thousands hours. One sulfur dose addition time ranges from 0.5 to 1.5 h.

EFFECT: increased yield of reforming catalysate.

3 cl, 1 tbl, 7 ex

FIELD: catalyst preparation methods.

SUBSTANCE: hydrodesulfurization catalyst is sulfidized in reflux-type reaction-distillation column in following consecutive stages: drying catalyst with inert gas; filling reaction-distillation column with sulfur-containing sulfidizing solvent; establishing hydrocarbon feedstock and hydrogen consumptions; starting recycling of sulfidizing solvent; heating reaction-distillation column to first temperature within a range of 300 to 500°F, which is higher than sulfidizing agent decomposition temperature; introducing sulfidizing agent; revealing by-product in top run, namely water azeotrope, and taking away water; monitoring breakthrough of sulfidizing agent into top run; raising temperature to second temperature within a range of 500 to 700°C and; maintaining said second temperature over a required period of time.

EFFECT: enhanced process efficiency.

14 cl, 2 dwg

FIELD: production of hydrorefining catalyst.

SUBSTANCE: the invention presents a method of production of hydrorefining catalysts, that provides for preparation of non-calcined catalyst for hydrorefining of hydrocarbonaceous raw materials polluted with low-purity heteroatoms. The method includes: combining of a porous carrying agent with one or several catalytically active metals chosen from group VI and group III of the Periodic table of elements by impregnation, joint molding or joint sedimentation with formation of a predecessor of the catalyst containing volatile compounds, decrease of the share of the volatile compounds in the predecessor of the catalyst during one or several stages, where at least one stage of decrease of the shares of the volatile compounds is carried out in presence of at least one compound containing sulfur; where before the indicated at least one integrated stage of decrease of the share of volatile compounds - sulfurization the indicated predecessor of the catalyst is not brought up to the temperatures of calcination and the share of the volatile compounds in it makes more than 0.5 %. Also is offered a not-calcined catalyst and a method of catalytic hydrorefining. The invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

EFFECT: the invention ensures production of a catalyst of excellent activity and stability at hydrorefining using lower temperatures, less number of stages and without calcination.

10 cl, 8 ex, 4 dwg

The invention relates to the production of liquid catalysts on the basis of aromatic sulfonic acids for the hydrolysis of fats

The invention relates to the field of petrochemical, refining, or rather to the catalysts used in the refining

FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention is dealing with development of effective catalyst for hydrogenation of unsaturated hydrocarbons (alkenes, alkynes) and a method for preparation thereof, which could be used in fine organic synthesis. Catalyst contains palladium compound and a modifying additive, the former being palladium bis-acetylacetonate and the latter phosphine (PH3) at molar ratio ranging from 1:0.1 to 1:1, respectively. Preparation of catalyst is based on reduction of palladium compound with hydrogen in presence of phosphine, which is introduced before reduction of palladium bis-acetylacetonate at catalytic system formation temperature: 70-80°C. Optimal time for molding of catalyst is 10-15 min.

EFFECT: increased catalytic activity when carrying out catalytic process under mild conditions (at room temperature and atmospheric pressure) and reduced catalyst preparation expenses.

2 cl, 5 tbl, 24 ex

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