The catalyst for catalytic reforming of gasoline fractions and the method of its preparation

 

(57) Abstract:

The invention relates to the refining and petrochemical industries. Described is a catalyst for catalytic reforming of gasoline fractions, which contains platinum, chlorine and the promoter is rhenium or tin - distributed on the surface of the carrier, where the carrier uses the volumetric composition of carbonaceous oxynitride aluminum, surface oxychloride and gamma-alumina, with the following ratios, wt.% in terms of dry substance: xinitrc aluminium 0,5-5,5; aluminium oxychloride 0,5-2,5; gamma-aluminum oxide - rest. It also describes the method of preparation of the catalyst. Technical result: the resulting catalyst has a high stability under harsh conditions. 2 AD. and 2 C.p. f-crystals, 1 table.

The invention relates to the refining and petrochemical industries and can be used in the manufacture of catalysts for the catalytic reforming of gasoline fractions.

The problem is deeper processing of oil and increase the selection of target products during the refining largely solved by improving the efficiency of catalytic p is the key catalysts - chemical, structural, textural, including in the preparation of media.

Known catalyst for reforming of gasoline fractions (EN 2145518, 1998.12.17, 01 J 23/42). The catalyst contains platinum, rhenium and chlorine oxide on the carrier. As the carrier is used, the composition of the oxides of aluminum, titanium and manganese in the mass ratio of Al2ABOUT3:Tio2:MnO2equal 1:(0,0002-0,05):(0,0004-0,0015).

Such a catalyst is not effective enough for use in the reforming process with the aim of obtaining catalyzate octane on the research method PP 96-100, resulting in the need for its operation at high temperatures (510-S) and short duration mezhregionalnogo cycle or excessive falling of the output liquid catalyzate (selectivity) during the cycle.

Known catalyst for reforming of gasoline fractions and how to obtain it (EN 2051736, 1993.12.28, 01 J 23/656). The catalyst contains, wt%: platinum 0,2-0,4, rhenium and 0.2-0.6 ammonium perrhenate 0.1 to 0.2, manganese oxide of 0.05-0.2, chlorine 0,8-1,5, alumina - rest. The catalyst was prepared by exposure-Al2ABOUT3in the solution of rhenium acid and salts of manganese at pH 4-6,0 at room temperature and atmospheres is 0.003 to 0.007 MPa and incubated for another 2 hours. The solution is drained, dried composition 6 h at 120C and kept in a current of dry air at 180C for 3 h at 500 ° C - 3 hours the Cooled composition is impregnated with an aqueous solution platinochloride-hydrogen, rhenium and hydrochloric acids.

The disadvantages of such a catalyst include the low resistance to the action of coke deposits, resulting in insufficient high selectivity and stability.

The problem to which the invention is directed, is to increase the octane number of petroleum gasoline fractions by creating a highly stable catalyst for reforming and method of its preparation. This will allow you to establish a constant production of gasoline-reformate octane (IOC) 96-99 points and even more when meregenerasikan cycle for at least one year (2-3 years) and to work steadily in the so-called hard mode at temperatures up to S without rapid decrease in activity and selectivity.

The problem is solved as follows.

The catalyst for catalytic reforming of gasoline fractions contains platinum, chlorine and the promoter is rhenium or tin - distributed on the surface of the carrier, and is characterized by the fact that as the carrier is used the composition of the volume of the m=310-4-0,67, p=0.006-0,64, surface oxychloride formula Al3(OH)5CLnwhere n=0,7-1,3, and gamma-alumina, with the following ratios, wt.% in terms of dry substance: Al3(OH)8(NO3)m(C)p0,5-5,5; Al2(OH)5Cln0,5-2,5; -Al2ABOUT3- the rest. In addition, the media total content of impurities of sodium, iron, sulfur, silicon dioxide, calcium and magnesium is not greater than 0.05 wt.%.

In addition, the carrier optionally modified by the addition of titanium dioxide in amounts of from 0.01 to 0.3 wt.%.

The method of preparation of the catalyst involves the stages peptization powder pseudoboehmite aluminum hydroxide, granulation, heat treatment of substrate, deposition of platinum, chlorine and promoter and heat treatment of the catalyst and is characterized by the fact that in the source material, choose powder pseudoboehmite aluminum hydroxide obtained from aluminum alcoholate brand Pural SB, and the obtained aluminum hydroxide is treated with a solution of citric and/or nitric acid for the formation of bulk carbonaceous oxynitride aluminum formula Al3(OH)8(NO3)m(C)pand obtained after calcinations at UB>mWITHp, treated with an aqueous solution containing HCl, to form a surface oxychloride formula Al2(OH)5CLn.

The purpose of the invention is achieved by using as a starting material powder of aluminum hydroxide pseudoboehmite patterns of high purity with a total impurity content of sodium, iron, silicon dioxide, calcium and magnesium not more than 0.05 wt.%, but containing added carbon (carbonate) and, possibly, titanium dioxide, and special treatments such powder with acid that allows you to create a volume of medium carbon xinitrc aluminum definite composition and on the surface of aluminium oxychloride particular composition. The carrier obtained in this way, treated with an aqueous solution of platinum compounds, promoter (rhenium or tin) and halogen (chlorine). Treatment of the carrier with a solution of hydrochloric acid may be combined with treatment with platinum compounds and promoter. Prepared in this way, the catalyst has higher value activity, selectivity and stability and enables to develop in the process of catalytic reforming catalysate octane Chi is the Cabinet of pseudoboehmite shown in the table.

The method of preparation of the catalyst involves the following stages:

- peptidase powder pseudoboehmite aluminum hydroxide by treatment with a solution of citric or nitric acid or their mixtures with continuous mechanical stirring;

- granulating the obtained plastic paste or pseudosasa media, respectively, by the method screw extrusion or drip molding;

- heat treatment of the freshly-formed pellets of extrudates or pellets, drying and calcination in a dehumidified air;

- processing of calcined carrier with a solution of hydrochloric acid (preferably combined with the next stage);

- coating the surface of the carrier aqueous solutions of the active compounds of components - platinum (platinochloride acid), promoter (ammonium perrhenate or chlorine tin) and chlorine (hydrochloric acid);

- heat treatment of the catalyst, drying and calcination in air flow.

The catalyst was tested in the process of catalytic reforming of straight-run hydrotreated broad gasoline fraction with a boiling within 85-180C and the following contents of the main classes of hydrocarbons, wt.%: aromaticheski is SS="ptx2">

First conduct the reforming of this material in soft mode: at temperatures of 470, 480, 490 and 510, respectively, 40-50, 20-25, 20-25 20-25 hours at a pressure of 1.5 MPa, the space velocity of the feedstock 1.5 h-1and the frequency of circulation of the hydrogen-containing gas (hydrogen-rich) 1500 N. L./l of raw material per hour. The total duration of the run in soft mode is about 4 days.

Then move to the hard mode in the following conditions: the temperature was raised to C, reduce pressure to 1.0 MPa, the volumetric feed rate increase to 2.0 h-1and the multiplicity of circulation all reduced to 1000 N. L./l of raw materials. The experience carried out for 100 hours.

The catalyst is characterized by the presence of aromatic hydrocarbons in catalyzate obtained at a temperature of 510, the selectivity value of the output liquid stable catalyzate content arenes 72 wt.%, and as a measure of stability take a drop of activity during trials in hard mode (with 20-to 100-th hour).

EXAMPLE 1:

Take 133,3 g powder pseudoboehmite brand Pural SB-1, characterized by the value of loss on ignition at 850 (SPT) equal to 25.0% of that in terms of Al2ABOUT3responsible 100,0, the Powder contains an additive of 0.3% TiO is RA Z-shaped blades and gradually in small portions with constant stirring add 120 cm3citric acid solution with a concentration of 7%. The total mixing time is 1 hour. Received a plastic mass ekstragiruyut on a screw press, and then dried on a belt dryer in the current of heated air at a temperature of 50-130C for 2 hours. The dried extrudates are subjected to calcination at a temperature of 650C in a stream of dry air, which is continuously served with a bulk velocity of 1000 h-1i.e. through the layer obtained 133,3 cm3the carrier extrudates miss 133,3 l of air per hour.

Get about 104 g of the medium, including its structure 110-4% carbonaceous oxynitride aluminum composition of Al3(OH)8NO0,0003(C)0,64and 0.3% of titanium dioxide (the rest is gamma-alumina). The total content of impurities in the carrier - Na2O, Fe, S, SiO2Ca, MD is 0.038 wt.%.

The carrier is brought into contact with 140 ml of aqueous impregnating solution containing 0,63 g H2PtCl6, 0,408 g HReO4, 2.2 ml of glacial acetic acid and 0.6 g of HCl. The impregnation is conducted for 2 hours under stirring, with 1 hour without external heating (or cooling to 5-10C) and 1 hour with heating at 75-80C. At the end of this operation, the solution is brought to a boil and evaporate hut is the temperature of about 150C in static conditions (in an oven) and calcined in a tubular reactor in a dehumidified air speed heating 25°C/hour; the temperature of 500C; blower speed 133,3 l/h; duration of calcination for 4 hours.

The catalyst composition (wt.% in terms of dry substance): 0,3 Pt; 0,3 Re; 0,3 TiO2; 1,1 Cl; the rest is media, which is a mixture of 110-4% carbonaceous oxynitride aluminum composition of Al3(01-1)8NO0,0003(C)0,64and 0.5% of the surface oxychloride composition of Al2(OH)5Clthe 2.5and gamma-Al2ABOUT3(the rest is up to 100%).

Before testing, the catalyst is reactivated by hydrogen at a temperature of 450-500 ° C, a pressure of 1.0 MPa and a flow of hydrogen 66,7 l/h for 4-5 hours.

Test results:

- activity - the content of aromatic hydrocarbons in catalyzate, the resulting experience at a temperature of 510 - 72 wt.%.

- selectivity - output stable catalyzate5+ with the content of aromatic hydrocarbons 72 - 87 wt.%.

the stability index of activity decline in hard mode 4 wt.%.

EXAMPLE # 2

Exactly the same as in example No. 1, take 133,3 g powder pseudoboehmite brand Pural SB-1 with the SPT equal to 25.0% of that in terms of Al2ABOUT3responsible 100,0, the Powder contains about 0.001% TiO2and traces of plural, using the method of drip molding (patent RF №2060819, 1994).

Calcined at a temperature of S ball carrier contains, calculated on the dry matter: of 0.8 wt.% oxynitride aluminum composition of Al3(OH)8(NO3)0,67(C)0,006, 0,001% TiO2, (rest-Al2ABOUT3). The total content of impurities in the carrier - Na2O, Fe, S, SiO2Ca, MD is 0,029 wt.%.

The carrier is brought into contact with 140 ml of aqueous impregnating solution containing 0,525 g H2PtCl6, 0,69 g SnCl4, 2.2 ml of glacial acetic acid and 1.2 g of HCl. The impregnation is conducted for 2 hours under stirring, with 1 hour without external heating (or cooling to 5-10C) and 1 hour with heating at 75-80C. At the end of this operation, the solution is brought to a boil and evaporate excess water for 2-3 hours, reaching a state of flowability of the catalyst. Next, the catalyst is dried at a temperature of about 150C in static conditions (in an oven) and calcined in a tubular reactor in a dehumidified air speed heating 25C/HR, temperature of 500C, the blower speed 133,3 l/h, the duration of calcination for 4 hours.

The catalyst composition (wt.% on dry substance): 0.25 Pt; 0,4 SnO2; 0,001 Tio23(OH)8(NO3)0,67(C)0,006and 0.5% of the surface oxychloride composition of Al2(OH)5Cl0,5and gamma-Al2ABOUT3(the rest is up to 100%).

Before the test, the catalyst was restored under conditions identical to example No. 1, and test according to standard methods, as described above.

Test results:

the activity of 72.5 wt.%;

the selectivity of 89 wt.%;

- stability 6 wt.%.

EXAMPLE # 3

The media in General, prepared as described in example No. 1, but with the following exceptions.

The original powder pseudoboehmite type Pural, as in example No. 1, contains 0.3% TiO2, a small amount of carbon and traces of nitrates is about 10-5%.

For peptization use a mixture of nitric and citric acid in aqueous solution, and the concentration of citric acid 4% nitrogen 3%, and the amount of solution taken equal to 140 ml per 133,3 g powder pseudoboehmite.

After shaping by extrusion, drying and calcination at a temperature of S carried out identical to example No. 1, receive about 104 g of the carrier, consisting of 0.1% carbon oxynitride aluminum composition of Al3(OH)8The N - Na2O, Fe, S, SiO2Ca, MD is 0,040 wt.%.

The carrier is brought into contact with 140 ml of aqueous impregnating solution containing 0,63 g H2tl6, 0,655 g NH4ReO4, 2.2 ml of glacial acetic acid and 0.45 g of Hcl. The impregnation is conducted for 2 hours under stirring, with 1 hour without external heating (or cooling to 5-10C) and 1 hour with heating at 75-80C. At the end of this operation, the solution is brought to a boil and evaporate excess water for 2-3 hours, reaching a state of flowability of the catalyst. Next, the catalyst is dried at a temperature of about 150C in static conditions (in an oven) and calcined in a tubular reactor in a dehumidified air speed heating 25C/HR, temperature of 500C, the blower speed 133,3 l/h, the duration of calcination for 4 hours. The catalyst composition (wt.% in terms of dry substance): 0,3 Pt; 0,45 Re; 0,3 TiO2; 1,15 Cl; else - the media, representing a mixture of 0.1% carbon oxynitride aluminum composition of Al3(OH)8NOof 0.2(C)for 0.4and 0.5% of the surface oxychloride composition of Al2(OH)5Cl-and gamma-Al2ABOUT3(the rest is up to 100%).

Before the test the catalyst to restore the conditions which SS="ptx2">

activity 73 wt.%;

- selectivity of 87.5 wt.%;

- stability 4 wt.%.

1. The catalyst for catalytic reforming of gasoline fractions containing platinum, chlorine and the promoter is rhenium or tin - distributed on the surface of the carrier, characterized in that as the carrier uses the volumetric composition of carbonaceous oxynitride aluminum formula Al3(OH)8(NO3)m(C)pwhere m=310-4to 0.67, p=0,0060,64, surface oxychloride formula Al2(OH)5Clnwhere n=0,7-1,3, and gamma-alumina, with the following ratios, wt.% in terms of dry substance:

Al3(OH)8(NO3)m(C)p0,5-5,5

Al2(OH)5Cln0,5-2,5

-Al2O3Else

2. The catalyst p. 1, characterized in that the carrier of the total content of impurities of sodium, iron, sulfur, silicon dioxide, calcium and magnesium is not greater than 0.05 wt.%.

3. The catalyst PP.1 and 2, characterized in that the medium is additionally modified by the addition of titanium dioxide in amounts of from 0.01 to 0.3 wt.%.

4. The method of preparation of the catalyst according to PP.1-3, which includes stages peptization powder omotola and heat treatment of the catalyst, and characterized in that the source material is chosen powder pseudoboehmite aluminum hydroxide obtained from aluminum alcoholate brand Pural SB, and the resulting aluminum hydroxide is treated with a solution of citric and/or nitric acid for the formation of bulk carbonaceous oxynitride aluminum formula Al3(OH)8(NO3)m(C)pand obtained after calcination at a temperature of 550-650C granules extrudates or spheres consisting of Al2O3and Al3(OH)8(NO3)mCp, treated with an aqueous solution containing model HC1, for the formation of surface oxychloride formula Al2(OH)5Cln.

 

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