Bismuth- and phosphorus-containing catalyst carriers, reforming catalyst based thereon, preparation method, and petroleum reforming process

FIELD: petroleum processing and catalysts.

SUBSTANCE: invention relates to bismuth- and phosphorus-containing catalyst carriers, petroleum reforming catalysts prepared on these carriers, to methods for preparing both carriers and catalysts, and to petroleum reforming process using these catalysts. Described are catalyst carrier containing γ-alumina particles wherein bismuth and phosphorus are distributed essentially uniformly in catalytically efficient concentrations and a method for preparation thereof comprising (a) preparing solution containing bismuth precursor and solution containing phosphorus precursor; (b) preparing γ-alumina/alumina sol mixture; (c) mixing mixture of step (b) with solutions prepared in step (a) to produce carrier precursor containing essentially uniformly distributed phosphorus and bismuth; (d) molding; and (e) drying and calcination. Invention also describes petroleum reforming catalyst containing above-defined carrier and catalytically efficient amount of platinum, chlorine, and optionally rhenium; method of preparation thereof; and petroleum reforming process after hydrofining, which involves contacting petroleum with above-defined catalyst in presence of hydrogen at elevated temperature and pressure.

EFFECT: reduced catalyst coking velocity and achieved high stable activity of catalyst.

25 cl, 6 dwg, 4 tbl, 10 ex

 

The SCOPE of the INVENTION

The invention relates to bismuth - and phosphorus-containing carriers for catalysts, reforming catalysts oil made from these carriers, methods of manufacture as carriers and catalysts, and a method of reforming of oil with the use of these catalysts.

The prior art INVENTIONS

Catalytic reforming of crude oil is one of the important ways of refining, through which oil is enriched in the low-octane paraffins and naphthenes into high-octane liquid product of the reforming enriched in aromatic compounds With5+, and hydrogen (H2). Constantly search for improved reforming catalysts with high selectivity (i.e. providing high outputs liquid fraction With5+ and H2), high activity, low speeds supervivencia and high stability, selectivity and/or activity. More selective catalysts are needed to maximize the production of valuable products, liquid product of reforming and H2at minimum output less valuable gaseous products1-C4. Also need catalysts with acceptable selectivity, but increased activity, as they allow you to work at lower temperatures at the entrance is into the reactor while maintaining the same level of conversion (octane) or allow you to work at the same temperature, but with a higher conversion (octane). In the first case, the increased activity of the catalysts also allows to significantly extend the duration of the cycle and to reduce the frequency of regeneration. Catalysts that nauglerozhivatelya with lower speeds and exhibit increased stability selectivity and/or activity, is also very necessary, because they allow to reduce considerably the time of burning coke and time of a full cycle and prolong the time before regeneration.

Many researchers are making efforts to develop improved catalysts for reforming. Originally in industrial catalysts used a platinum group metal, preferably itself platinum deposited on a carrier of γ-alumina, acidified with halogen (see, e.g., Haensel, Universal Oil Products Company) U.S. patent No. 2479109-110 issued in 1949). Around 1968 it was proposed to use rhenium together with platinum. Kluksdhal, U.S. patent No. 3415737, offers the catalysts Pt/Re, in which the atomic ratio of rhenium to platinum is from 0.2 to 2.0, and U.S. patent No. 3558477 indicates the importance of maintaining the atomic relations of rhenium to platinum of less than 1.0. In the patent Buss (U.S. patent No. 3578583) is proposed to include iridium in small quantities, up to 0.1%, the catalyst containing 0.3% rhenium and platinum. Gallagheret al., U.S. patent No. 4356081, offers bimeta the symbolic reforming catalyst, in which the atomic ratio of rhenium to platinum is in the range from 2 to 5.

At least since 1959 that the phosphorus in the composition of the reforming catalyst increases the yield of aromatic compounds as claimed Haensel in U.S. patent No. 2890167. In U.S. patent No. 3706815 Alley showed that the introduction of hepatoblastoma ions, hepatoblastoma noble metals of group VIII, in the form of polyphosphoric acid in the catalyst increases isomerizing activity. Antoset al. in U.S. patent No. 4367137, 4416804, 4426279 and 4463104 argued that the addition of phosphorus to the reforming catalyst based on a noble metal increases the outputs of hydrocarbons5+.

In 1974-5, Wilhelm, U.S. patent No. 3798155, 3888763, 3859201 and 3900387, showed that the introduction of bismuth in the reforming catalyst containing a platinum group metal, improves the selectivity, activity and stability of catalysts. Antos, U.S. patent No. 4036743, proposed a catalyst for conversion of hydrocarbons, containing platinum, bismuth, Nickel, and halogen. Recently Wuet al., U.S. patent No. 6083867 and 6172273 B1, suggested reforming catalyst mixed composition or produced in several stages, the catalyst containing the first catalyst of platinum and rhenium on a porous carrier, and a second catalyst containing bismuth and silicon oxide.

However, so far no one has pointed to the benefits of introducing as bismuth and phosphorus the reforming catalyst oil on the basis of precious metal.

The INVENTION

The invention provides a carrier for a catalyst containing γ-aluminum oxide and small amounts of bismuth and phosphorus included in the media uniformly distributed on it condition. In addition, the invention provides compositions of catalysts containing platinum, chlorine and optionally rhenium deposited on a specified media. The invention also provides a method of manufacturing such carriers for catalysts and compositions of the catalysts for the reforming process oil in the presence of these catalysts to increase its octane number. When using Bi - and P-containing catalysts of the present invention in the catalytic reforming of oil suddenly found that they are characterized by lower speeds supervivencia and reduce outputs5+ and activity, i.e. increased stability compared with catalysts containing only or Bi or R, formerly known.

BRIEF DESCRIPTION of DRAWINGS

Fig. 1 shows the data reduction output5+ on the catalysts a to H.

Fig. 2 shows the data reduction activity of catalysts a to H.

Fig. 3 shows the data reduction output5+ steamed and oxychlordane catalysts DSOand GSO.

Fig. 4 shows the data on the mind is isenia activity steamed and oxychlordane catalysts D SOand GSO.

Fig. 5 shows the data reduction output5+ on the catalysts from I to L.

Fig. 6 shows the data reduction activity of catalysts from I to L.

DETAILED DESCRIPTION

Compositions carriers for catalysts of the present invention include aluminum oxide, preferably γ-aluminum oxide, which introduced a small amount of bismuth and phosphorus during extrusion cooking the mixture for the media. It was found that the catalysts prepared from such media with the introduction of small amounts of bismuth and phosphorus, uniformly distributed in the medium significantly increased output With5+ and increased stability compared to conventional compositions of the catalysts. In addition, these promoters in the media significantly reduces the rate of supervivencia and increase the ability of the catalyst to regenerate after exposure to moisture.

The composition of the catalysts according to this invention include the media, impregnated with a catalytically active amounts of platinum and chlorine and, optionally, a catalytically active amount of rhenium. A catalytically effective amount of Pt in the catalyst creates the desired ability of the catalyst to work in the reaction of hydrogenation-dehydrogenation, a catalytically effective amount Re (when he precuts is there) increases resistance to coxworthy and decontamination, and a catalytically effective amount of Cl increases the acidity of the medium, which is responsible for the reactions of isomerization and cracking. The introduction of Pt, Re and Cl in the catalyst reforming oil is well known in this field. However, when these elements are introduced by impregnation in the media of the present invention, these catalysts are observed much less speed supervivencia, higher outputs With5+ and stability activity than the catalysts containing the same elements, introduced by impregnation in traditional media. Therefore, the compositions of the catalysts of the present invention can reduce the frequency of regeneration of the catalyst and to maximize its running time, the product of reforming and profitability. In rare cases where increased stability is not needed, these compounds provide significant savings due to reduced speeds supervivencia, more rapid burning of the coke and the reduced time of a full cycle during regeneration compared with conventional catalysts. Reduced speed supervivencia compositions of this invention would be a big advantage for processors operating with units of the fixed bed reforming units of two different types: circular and plurigenera.

The carrier for the catalyst of the present invented what I includes aluminum oxide, preferably γ-alumina, with effective amounts of uniformly distributed bismuth and phosphorus.

Effective amounts of bismuth and phosphorus are distributed in the particles of the medium through the introduction of these promoters in the mixture of the precursor of the medium before the formation of the particles of the medium, which is usually carried out by extrusion. It has been found that an effective amount of bismuth is in the range from 0.05 wt.% to 0.1 wt.% in the calculation of the final catalyst, preferably from 0.05 wt.% to 0.08 wt.%. It was found that the effective amount of phosphorus is in the range from 0.05 wt.% to 0.6 wt.% in the calculation of the final catalyst, preferably from 0.1 wt.% to 0.4 wt.% and particularly preferably from 0.25 wt.% to 0.35 wt.%.

The carrier particles can be molded by any method known in this field. In the preferred method of preparing a mixture containing about 62 wt.% powder γ-aluminium oxide and 38 wt.% Zola aluminum oxide. γ-aluminum Oxide is a γ-alumina of high purity, prepared by dissolving aluminum wire in acetic acid, followed by curing to the formation of the Sol of aluminum oxide and spray drying Zola with the formation of the alumina powder. The Sol of aluminum oxide receive, as described above (i.e. by dissolving aluminum wire in acetic Ki the lot and curing), and it contains about 10 wt.% alumina (dry basis), 3 wt.% acetic acid and the rest is deionized water. The Sol of aluminum oxide is mixed with alumina powder, and it is peptizyme reagent during extrusion γ-aluminium oxide. Any other ways (without using the Sol of aluminum oxide, for example, using additives for extrusion), known to specialists in this field can also be used to obtain carrier particles of aluminum oxide according to the present invention. Such additives for extrusion include, but are not limited to, acids (e.g. nitric, acetic, citric, etc. and/or organic additives for the extrusion (for example, metozel(methylcellulose), PVI (polivinilbutilovy ether), branched (steric) alcohols and so on).

The desired amount of phosphorus and bismuth injected into the received media essentially homogeneous, adding in mixed Sol γ-aluminium oxide/aluminium oxide a solution of the precursor of phosphorous in a quantity sufficient to obtain the desired concentration of phosphorus on the destination media, and then a solution of the precursor of bismuth in an amount sufficient to obtain the desired concentration of bismuth on the destination media. Solutions of phosphorus and bismuth added slowly followed by prolonged stirring to ensure that the Homo is i.i.d. distribution of phosphorus and bismuth in the media. The final mixture should be prepared in the form of a paste suitable for extrusion. Suitable for the extrusion of pasta has index LOI (loss on ignition) from 30 to 70 wt.% and more preferably in the range of 45-60 wt.%.

To enter the desired amount of phosphorus in the media, prepare a solution of a precursor of phosphorus. The solution can be prepared by any means known in this field. The precursor of the phosphor is chosen from the group consisting of phosphorus-containing acid or salt, for example, N3RHO4N3RHO3N3RHO2, NH4H2PO4, (NH4)2HPO4the most preferred N3RHO4. The preferred solution of the precursor may contain from 50 to 85 wt.% H3RHO4most preferably in the range of 70-85 wt.%.

To enter the bismuth in the media in a way that would ensure a homogeneous distribution of atoms of bismuth, it is important to use a solution of bismuth containing all of the bismuth cations in solution in the absence (through chemical bonds with other elements) indirect interactions between them. You can use many predecessors bismuth, including, but not limited to, Bi(NO3)3.5H2Oh, BiCl3, BiOCl, BiBr3acetate Bi citrate Bi and various alcoholate Bi, and most preferred is Bi(NO 3)3.5H2Acting For the preparation of Bi-containing media and catalysts of the present invention can be used solutions of precursors in water systems water + complexing reagents (to improve solubility Bi), acidified aqueous solutions, and solutions of various surfactants or organic solvents. Acceptable concentration of bismuth in the solution depend on the selected predecessor bismuth, nature of solvent and the solubility of the precursor in the solvent. The most preferred solutions of bismuth containing about 9 wt.% Bi (Bi(NO3)3.5H2About) and about 10 wt.% d-mannitol (complexing agents), and the rest water. You can also use other complexing agents or hepatoblastoma reagents, including, but not limited to, polynuclear alcohols, mixtures of polynuclear alcohols or alcohols and acids, instead of d-mannitol for the complete dissolution of the bismuth precursor in the solvent. The same effect can be obtained by using acidified aqueous solutions of bismuth precursor.

The final stage of preparation of the carrier of the present invention consists in forming the paste obtained as described above, the particles of the carrier, followed by drying and calcination. You can apply tra the investment in the form of particles, for example, spheres, extrudates in the form of cylinders and shamrocks, etc. of the Obtained particles can be dried by any means known to specialists in this field. However, the preferred drying at low temperature, i.e. from 110°to 140°C, for 10 hours. After drying should get the media level LOI in the range of from 10 wt.% to 36 wt.%, more preferably from 17 wt.% to 36 wt.%. Preferably dried particles of the medium to be ignited to reduce the LOI to a value of from 1 wt.% up to 10 wt.%, preferably from 1 wt.% to 7 wt.%. The calcination is carried out at a temperature of 400°750°C, preferably from 550°700°With, in the course of time from 30 minutes to 5 hours, preferably from 1 hour to 2 hours.

The received media of the present invention are characterized by substantially uniform distribution of bismuth and phosphorus in native material - γ-aluminium oxide.

Catalysts

To obtain the final catalyst of the present invention the catalytically active amounts of platinum and chlorine and, optionally, rhenium is applied to the carrier by impregnation, well-known experts in this field. It was found that the effective amount of platinum from 0.1 wt.% to 1.0 wt.% in the calculation of the final catalyst, preferably from 0.15 wt.% to 0.6 wt.% and particularly preferably from 0.20 wt.% to 0.30 wt.%. Was naide is about, how effective is the amount of chlorine from 0.05 wt.% up to 2.0 wt.% in the calculation of the final catalyst, preferably from 0.8 wt.% to 1.2 wt.% and particularly preferably from 0.9 wt.% up to 1.1 wt.%. If rhenium is present, the effective amount of rhenium from 0.01 wt.% to 1.0 wt.% in the calculation of the final catalyst, preferably from 0.1 wt.% to 0.5 wt.% and particularly preferably from 0.2 wt.% to 0.45 wt.%.

For preparation of the impregnating solution and impregnation of the carrier of the present invention can use various predecessors Pt, Cl and Re known to specialists in this field. Such precursors include, but are not limited to, hexachloroplatinum (hexachloroplatinic) acid, hexabromobenzene acid, chloroplatinic ammonium, tetrachloroplatinate, dinitrodiphenylamine, hydrochloric acid, carbon tetrachloride, methyl chloride, dichloromethane, 1,1,1-trichloroethane, ammonium chloride, rhenium acid and ammonium perrhenate. Fits any predecessor, which decomposes in water to form the desired ions, otlichayuschihsya on the media. In addition, the impregnating solution may contain small amounts of various acids such as nitric, carbonic, sulfuric, citric, formic, oxalic, etc. that are known to specialists in this area, improve the allocation of platinate in the case of rhenium - perranuthnoe on a carrier of alumina. Concentrations of Pt, Cl and optionally Re in the impregnating solution is chosen in such a way as to obtain the desired concentrations of these components in the final catalyst. For the preparation of catalysts of this invention can use any impregnation techniques known to experts in this field.

Method of reforming oil

The reforming of crude oil after hydrotreatment is carried out by contacting the feedstock with the catalyst of the present invention in the presence of hydrogen at elevated temperature and pressure. Operating conditions include a space velocity in the range of from 0.5 h-1up to 6 h-1preferably from 1 h-1up to 3 h-1pressure in the range of from about 0.1 MPa to about 3.5 MPa, preferably 1 MPa to 3 MPa, and a temperature from about 315°C to about 550°C, preferably from 480°With up to 540°C, the ratio of recirculated gaseous hydrogen to the hydrocarbon feedstock is from about 1 mol/mol to 10 mol/mol, preferably from 1.5 mol/mol to 8 mol/mol and more preferably from about 2 mol/mol to 6 mol/mol.

EXAMPLES

The examples illustrate the preparation of media and catalysts according to this invention. The examples illustrate the use of these catalysts for reforming of oil and allow to compare their activity with actively is part of traditional catalysts for reforming of oil. These examples do not limit the scope of this invention.

EXAMPLE 1

This example describes the preparation of five carriers for catalysts of the present invention with different concentrations of bismuth.

The media was prepared by mixing 1 kg γ-aluminium oxide with 627 g Sol of aluminum oxide in the mixer for 10 minutes. While the mixer was slowly added to 9.1 g of 85 wt.% H3PO4and continued stirring for 1 minute. Then the mixer was added a solution of bismuth, are given in Table 1 for media and continued stirring for another 7 minutes to form a paste suitable for extrusion. The pasta was extrudible into pellets with a diameter of 1.6 mm, which was dried at 125°With during the night. The pellets were then cut into pieces 4-6 mm long and progulivali at 660°C for 1.5 hours. The resulting carrier And had the composition given in table 1.

Carriers b, C, D and E were prepared similarly, except that the solution a was replaced with the solution corresponding to each carrier, as shown in table 1.

Table 1
MediaAndInWithDE
Solution
g Bi(NO3) 35H2O3,201,871,491,120,747
g

d-mannitol
1,500,900,720,540,36
deionized H2O10,06,04,53,52,5
The final medium
Bi, wt.%0,170,100,080,060,04
P, wt.%0,30,30,30,30,3
Al2O3restrestrestrestrest

A small portion of the carrier D was sliderule, placing a few granules on the bottom of a glass Petri dishes and adding a drop of 20 wt.% solution of ammonium sulfide, and then closed with a glass lid and leave the pellets to come into contact with the pairs of ammonium sulfide for about 10 minutes During this treatment, the bismuth atoms in the extrudate reacted with ammonium sulfide with the formation of dark grey sulphide of bismuth. Look sulfatirovanne granules are uniformly colored in dark gray color, unlike the milk-white disulfid the skilled granules, that confirms a uniform distribution of atoms of bismuth in the media.

EXAMPLE 2

(Comparative)

This example describes the preparation of three traditional carriers for catalysts, and the carrier F is an aluminum oxide containing bismuth in the same concentration as the carrier D in Example 1, i.e. 0.06 wt.%; the carrier G is an aluminum oxide containing phosphorus in the same concentration as the media in example 1, i.e. 0.3 wt.%; and the carrier H is a pure aluminum oxide.

Carrier F was prepared according to the method described in Example 1, except that did not add H3PO4. Carrier G was prepared according to the method described in Example 1, except that no solution was added Bi/d-mannitol. The carrier H was prepared in the same way, but without the additives H3PO4and d-mannitol.

EXAMPLE 3

The example describes the preparation of the five catalysts of the present invention with different concentrations of bismuth in the media.

Five impregnation the catalysts were prepared by mixing of 0.77 ml of concentrated HNO3, 1.97 ml of concentrated (12M) HCl and 0,660 g of a solution of hexachloroplatinic acid (29,7 wt.% Pt) and 30 ml of deionized water. The solutions were mixed and added another 120 ml of deionized water to maintain the total volume of each impregnating solution is equal to 150 ml of the ATEM solutions were placed in a graduated cylinder 500 ml and stirred circulation using a peristaltic pump. In addition, through the solution was barbotirovany CO2with a very low speed using a bubbler tube that is placed in the bottom of the graduated cylinder. This was done in order to introduce anions HCO3-which, as is well known to specialists in this field, able to compete with anions Pt and Re for the centers on the surface of aluminum oxide and lead to a better distribution of these metals on a carrier of alumina.

For impregnation of each of the carriers a to E of Example 1 continued circulation of the solution and bubbling CO2and the solution in the cylinder quickly added 70 g of the carrier. Then impregnating solution was stirred circulation over the media for 3 hours while bubbling CO2and then supply CO2and the circulation stopped. The solution was decanted and the catalyst was dried at 125°C for 2 h, at 250°C for 4 h and then was progulivali at 525°for 1.5 hours Each of the obtained catalyst, designated as catalyst a-E in accordance with the native a-E, were analyzed and found to contain about 0.25 wt.% Pt, about of 0.95 wt.% Cl and corresponding number of Bi and P (see Example 1, table 1).

EXAMPLE 4

(Comparative)

This example describes the preparation of three traditional catalysts.

Prepared three impregnating solution. These solutions were identity is s solutions, prepared in Example 3, except that used 0,754 g of a solution of hexachloroplatinic acid instead 0,660 g in Example 3. Traditional media F, G and H of Example 2 was impregnated with these solutions as in Example 3. The analysis of the catalyst showed that the catalyst F contained about to 0.30 wt.% Pt and 1.0 wt.% Cl in media containing 0.6 wt.% Bi, catalyst G contained about to 0.30 wt.% Pt and 1.0 wt.% Cl in media containing 0.3 wt.% R, and catalyst H contained about to 0.30 wt.% Pt and 0.96 wt.% Cl in medium containing neither Bi nor R.

EXAMPLE 5

This example describes the processing steam and regeneration by oxychlorination process of catalyst D of Example 3 and G catalyst from Example 4.

Steam treatment: 40 g of catalyst D and G was placed in a boat made of stainless steel and then into the oven with programmable heating with lines of input and output. The furnace was closed and passed a current of air through the line and chamber of the furnace. The oven temperature is uniformly raised from room temperature up to 500°while maintaining air flow. On reaching 500°With the current of air is switched off and set the slow current of water through the inlet line into the heated chamber of the furnace. The water evaporated in the furnace chamber and formed water vapor. Samples of the catalysts were treated with steam in an oven for 16 h to significant agglomeration of Pt. Then feed in the s stopped, turn off the heat and again missed the air. The samples were cooled to 150°and carried in an airtight container. Although the agglomeration of Pt occurred in both samples, steamed catalyst D was much lighter than the steamed catalyst G (which was more dark gray), indicating increased resistance Pt to agglomeration in the catalyst D of this invention containing Bi and P.

The oxychloination: After steam processing both catalyst were subjected to two-step oxychloination. It is known that these treatments can restore the original high dispersion of Pt on alumina, and is widely used by specialists in this area to restore the dispersion of Pt, activity and selectivity of exhaust Pt-catalysts reforming. In the first phase through the catalyst bed to allow gas containing 2 mol.% O2/N2plus gaseous Cl2with pairs of N2Oh and HCl, 500°for 5.5 hours At the second stage, the gas was shut off and was passed through the catalyst layer, a gas containing 2 mol.% O2/N2with pairs of N2Oh and HCl, for another 5.5 hours the Purpose of the first phase of redispersion Pt on the media to the same dispersion as in freshly prepared catalyst, while the goal of the second stage was to bring the chlorine up to the desired level. robotany ferry oxymoronically sample of catalyst D is designated as catalyst D SOand the sample of catalyst G, treated similarly, denoted as GSO. Visually catalyst DSOdid not contain grayish colored granules, which indicates the absence of agglomeration of Pt. On the contrary, the catalyst GSOcontained grayish colored granules. This indicates that the catalyst D of the present invention containing Bi and P, better saves and restores the dispersion of Pt in the processing of water vapor and oxychloination than traditional catalyst G containing phosphorus, but not bismuth. Both catalysts were analyzed and it was found that they contain similar amounts of Cl (0,83 wt.% and 0.81 wt.% respectively.

EXAMPLE 6

This example describes the preparation of Pt - and Re-containing catalyst according to this invention.

An impregnating solution was prepared from 0,50 ml of concentrated HNO3, 1.89 ml of concentrated (12M) HCl and 0,660 g of a solution of hexachloroplatinic acid (29,7 wt.% Pt), 0,302 g NH4ReO4and 50 ml of deionized water. The solution was mixed and added deionized water to maintain the total volume of solution equal to 150 ml of the Solution was placed in a graduated cylinder 500 ml and stirred circulation using a peristaltic pump. In addition, through the solution was barbotirovany CO2with a very low speed using a bubble tube, placed the military in the bottom of the graduated cylinder. As soon as the circulation of the solution and bubbling CO2stopped, to the impregnating solution was added 70 g of the carrier D of Example 1. Then impregnating solution was stirred circulation over the media for 3 hours while bubbling CO2and then supply CO2and the circulation stopped. The solution was decanted and the catalyst was dried at 125°C for 2 h, at 250°C for 4 h and was progulivali at 525°for 1.5 hours In the resulting catalyst is designated as catalyst I, was found by analysis to about 0.25 wt.% Pt, 0.26 wt.% Re, 0.99 wt.% Cl, 0.06 wt.% Bi to 0.30 wt.% P and the rest is aluminum oxide.

EXAMPLE 7

(Comparative)

This example describes the preparation of samples of Pt - and Re-containing catalysts in traditional media F, G and H of Example 2.

The media samples F, G and H was soaked with a solution by the method described in Example 6. The catalyst obtained from the carrier of F, denoted as catalyst J was analyzed and found 0.26 wt.% Pt, 0.25 wt.% Re, 0.3 wt.% R and 0.98 wt.% Cl. The catalyst obtained from the carrier of N, denoted as L catalyst was analyzed and found to 0.25 wt.% Pt, 0.25 wt.% Re and 0.96 wt.% Cl.

In the following examples 8-10 describes the measurement and comparison of the activity of the catalysts prepared as described above. When assessing the activity of the catalysts in the reforming of oil used is ovali four term - the selectivity, activity, stability and speed supervivencia:

"Selectivity" is a measure of the yield of liquid products5+expressed as a percentage of the volume of fresh liquid raw materials.

"Activity" is a measure reactor temperature required to obtain the octane number of the target product.

"Stability" is a measure of the ability of the catalyst to maintain the selectivity and activity over time. Is expressed by a value inversely proportional to the speed reduction of selectivity and activity.

"Speed supervivencia" is a measure of the tendency to the formation of coke on the catalyst surface during the reforming process. Since the reforming catalysts are deactivated by the mechanism of coke formation on catalysts with lower speeds supervivencia usually have lower outputs5+ and the speed of decreasing the activity; that is, these catalysts have a higher stability than the catalysts with higher speeds supervivencia.

EXAMPLE 8

(Comparative)

This example illustrates a comparison of the activity of catalysts a to H in reforming full fraction (hydrocarbons With5-C12industrial raw oil after hydrotreatment with the content of the component with respect to the paraffins/naphthenes/aromatice the Kie connection (P/N/A) equal 51/34/15 wt.% respectively.

All experiments were performed in microreactors stainless steel, working in pseudoanabaena mode with a single pass H2and equipped with tanks for raw materials and products and gas chromatography analyzer on all products (N2+ hydrocarbons With1-C12). The catalysts were loaded into the microreactors in the form of whole particles (not crushed). Each experience has loaded 38 cm3catalyst and 38 cm3SiC (inert diluent) in four stages, as shown in table 2.

Table 2
StageThe catalyst, cm3SiC cm3
1 (input)1,917,1
2the 5.713,3
311,47,6
4 (output)19,00

Raw materials modified with isopropyl alcohol and 1,1,1-trichloroethane to get in the gas phase the desired level of 20 ppm by weight of N2About 1 ppm by weight Cl. "Excess" (junk) water is removed from the raw material to the experience, passing the raw material through a vessel filled with molecular sieves 4Å. The tests were carried out as experiments on decontamination (stability) at a constant octane h is the following (99S 5+RON octane number by the research method) at flow rate of liquid supply 2.4 h-1, 1,03 MPa and 3 mol H2/mole of hydrocarbon. These conditions, as mentioned above, the method of loading the catalyst, were selected in order to create a more hard working conditions of the catalyst and faster deactivation. To maintain the octane number of the product (C5+RON) at a constant level during the experiment, the temperature of the walls of the reactor were installed in such a way as to correct a reduction in activity.

Fig. 1 and 2 show a decrease in output With5+ and the temperature of the walls of the reactor (fall activity), respectively, for catalysts a to H. Table 3 shows the corresponding activity, decrease output With5+ and speed supervivencia. Analysis of the obtained data shows that the Bi-containing catalyst F is characterized by the lowest values of speed supervivencia, reduce output5+ and activity (i.e. the highest stability among traditional catalysts. Comparison of the data for catalysts G and H also shows that the addition of R to the carrier improves the outputs From5+, but the drop of activity and speed of supervivencia close to the values for catalyst H, printed on pure alumina. Therefore, the addition of one P not podavlyauschaya and does not improve the stability of reforming catalysts. On the contrary, the comparison of the reduction in the activity of Bi - and P-containing catalysts of the present invention shows that the speed of their supervivencia and fall activity is strongly dependent on the concentration of Bi. Surprisingly, the catalysts b, C and D, containing from 0.10 wt.% to 0.06 wt.% Bi and 0.3 wt.% R, there is a much lower speed supervivencia, reduce outputs5+ and activity, i.e. these catalysts have higher stability as compared with catalysts on carriers containing only Bi, only R and pure aluminum oxide, i.e. catalysts F, G and H. These data show that the introduction of suitable concentrations of Bi and P in the medium used for the preparation of catalysts for reforming of oil leads to a favourable synergistic effect in influencing the speed of supervivencia and stability of activity.

Table 3

Average hourly speed reduction
CatalystPt/Bi/P, wt.%Activity °S/hExit C5+about. %/hSpeed supervivencia, wt.%/h
A0,25/0,17/0,3+0,357-0,069+0,074
B0,25/0,1/0,32+0,270-0,043+0,058
C0,25/0,07/0,28+0,270-0,034+0,054
D0,26/0,06/0,29+0,258-0,045+0,052
E0,26/0,04/0,3+of 0.332-0,056+0,068
F0,24/0,06/0+0,300-0,054+0,061
G0,3/0/0,3+0,458-0,087+0,072
H0,3/0/0+0,390-0,095+0,074

Traditional catalysts of the type catalysts F, G and H first use in cyclic reforming apparatus, where they work in very harsh conditions (low pressure and sometimes high levels of humidity in the gas recycle). Under these conditions the speed of supervivencia much higher, i.e. rapid decontamination and requires frequent (every 1-2 weeks) regeneration. Catalysts b, C and D of the present invention allow to obtain significantly higher yields and stable activity and longer service life between regenerations compared with conventional catalysts. In addition, in rare cases, when you don't need a longer experiments, the catalysts of the present invention will significantly reduce the time of operations in which jihane coke and regeneration reactor, that will increase the time of operation and higher margins.

EXAMPLE 9

(Comparative)

This example compares the activity of the steamed and oxychlordane catalysts DSOand GSOExample 5.

Working conditions and loading of the catalysts were the same as in Example 8. Figures 3 and 4 show curves reduce the release of hydrocarbons From5+ and activity, respectively, obtained in these experiments. These experiments show that the catalyst DSOnoticeably superior to conventional catalyst GSObecause in the presence of the catalyst decrease output With5+ and activity is much less, as well as speed supervivencia, and outputs5+ and stability of the catalyst is significantly higher than in the fresh catalysts (see Example 8). This fact suggests that after staying in the unit with a very high humidity level Pt dispersion and activity of catalyst D of the present invention will be restored much easier (regeneration)than these options traditional catalyst G.

EXAMPLE 10

(Comparative)

This example compares the activity of Pt and Re-containing catalyst of the present invention (catalyst I of Example 6) and conventional Pt - Re-containing catalysts (catalysts J, K and L from the Use of the and 7).

Samples of all four catalysts used for reforming full faction industrial oil after Hydrotreating with respect to the components P/N/A equal 66/21/13 wt.% respectively. Experiments were performed on the same equipment and under the same conditions as described in Example 8. Figures 5 and 6 show the curves of change of output With5+ and the wall temperature of the reactor (fall activity), respectively, for catalysts I to L. table 4 shows the speed reduction activity and exit With5+and speed supervivencia.

Analysis of the obtained data shows that catalyst I of the present invention are observed much less speed supervivencia and reduce output5+ and activity, resulting in a higher stability compared to traditional catalysts J and L. Thus, the data clearly show that the addition of Bi and P to the carriers of catalysts containing noble metals, in the required concentrations leads to a synergistic increase in activity of the catalysts. Obviously, in the presence of a catalyst I installation reforming unit will operate at much lower temperatures for the same output With5+ and the desired octane number (conversion). In addition, in this particular case, the catalyst I will significantly extend the duration of the run, i.e. uvelichitsia full cycle and the profitability of the installation. Catalyst I also gives the opportunity to increase the profitability of the reforming apparatus by increasing the capacity of the device (volumetric feed rate), operating at an acceptable temperature at the inlet of the reactor and, thus, producing more liquid product of the reformer with the same octane number per unit time, as traditional catalytic systems. Catalyst I would be especially valuable for reforming apparatus, which are limited in activity.

Table 4

Average hourly speed reduction
CatalystPt/Bi/P, wt.%Activity °S/hExit C5+,

about. %/h
Speed supervivencia, wt.%/h
I0,25/0,26/0,06/0,3+0,184-0,016+0,070
J0,26/0,24/0,06/0+0,284-0,035+0,076
K0,25/0,25/0/0,3+0,247-0,020+0,074
L0,25/0,25/0/0+0,281-0,027+0,075

1. The carrier for the catalyst containing particles γ-aluminium oxide, which is essentially uniformly distributed bismuth is phosphorus in a catalytically effective concentration.

2. The carrier for the catalyst according to claim 1, in which the concentration of bismuth is in the range from 0.05 to 0.1 wt.%, and the concentration of phosphorus is in the range from 0.05 to 0.6 wt.%.

3. The carrier for the catalyst according to claim 1, in which the concentration of bismuth is in the range from 0.05 to 0.1 wt.%, and the concentration of phosphorus is in the range from 0.1 to 0.4 wt.%.

4. The carrier for the catalyst according to claim 1, in which the concentration of bismuth is in the range from 0.05 to 0.1 wt.%, and the concentration of phosphorus is in the range from 0.25 to 0.35 wt.%.

5. The carrier for the catalyst according to claim 1, in which particles obtained by extrusion.

6. A method of manufacturing a carrier for catalyst, including:

a) preparation of the solution containing the precursor of bismuth, and of the solution containing the precursor of phosphorus;

b) preparation of a mixture of γ-alumina and Sol of aluminum oxide;

c) mixing the mixture obtained in stage (b)with the solution prepared in stage (a), to obtain the predecessor of media containing essentially uniformly distributed phosphorus and bismuth;

d) forming particles of the precursor of the media and

e) drying and calcination of the particles.

7. The method according to claim 6, in which the bismuth precursor is chosen from the group consisting of Bi(NO3)3·5H2O, BiCl3, BiOCl, BiBr3, acetate Bi is itrate Bi and alcoholate Bi.

8. The method according to claim 6, in which the bismuth precursor is Bi(NO3)3·5H2O.

9. The method according to claim 6, in which the precursor of phosphorus selected from the group consisting of H3PO4N3RHO3N3PO2, NH4H2PO4and (NH4)2HPO4.

10. The method according to claim 6, in which the precursor of phosphorus is H3PO4.

11. The method according to claim 6, in which the mixture γ-alumina and Sol of aluminum oxide contains about 62 wt.% γ-alumina, and the rest of the Sol of aluminum oxide.

12. The carrier for the catalyst obtained by the method according to claim 6.

13. The reforming catalyst oil containing a carrier for a catalyst according to claim 1 and a catalytically effective amount of platinum and chlorine.

14. The catalyst according to item 13, additionally containing a catalytically effective amount of rhenium.

15. The catalyst according to item 13, in which the amount of platinum is in the range from 0.1 to 1% by weight of catalyst and the amount of chlorine is in the range from 0.05 to 2 wt.% by weight of the catalyst.

16. The catalyst according to item 13, in which the amount of platinum is in the range from 0.15 to 0.6% by weight of catalyst and the amount of chlorine is in the range from 0.8 to 1.2 wt.% by weight of the catalyst.

17. The catalyst according to item 13, in which the amount of platinum is in the range from 0.2 to 0.3 % by weight of the catalysis of the Torah and the amount of chlorine is in the range from 0.9 to 1.1% by weight of the catalyst.

18. The catalyst according to item 13, in which the amount of platinum is in the range from 0.1 to 1% by weight of catalyst and the amount of chlorine is in the range from 0.05 to 2% by weight of a catalyst where the catalyst additionally contains from 0.01 to 1 wt.% rhenium.

19. The catalyst according to item 13, in which the amount of platinum is in the range from 0.15 to 0.6% by weight of catalyst and the amount of chlorine is in the range from 0.8 to 1.2% by weight of a catalyst where the catalyst additionally contains from 0.1 to 0.5 wt.% rhenium.

20. The catalyst according to item 13, in which the amount of platinum is in the range from 0.2 to 0.3% by weight of catalyst and the amount of chlorine is in the range from 0.9 to 1.1% by weight of a catalyst where the catalyst further comprises from 0.2 to 0.45 wt.% rhenium.

21. The catalyst according to item 13, in which the concentration of bismuth in the carrier for the catalyst is in the range from 0.05 to 0.1% by weight of the catalyst and the phosphorus concentration in the carrier for the catalyst is in the range from 0.25 to 0.35 wt.%; and

the amount of platinum is in the range from 0.2 to 0.3% by weight of catalyst and the amount of chlorine is in the range from 0.9 to 1.1% by weight of the catalyst.

22. The catalyst according to item 13, in which

the concentration of bismuth in the carrier for the catalyst is in the range from 0.05 to 0.1% by weight of the catalyst and concentration of phosphorus in the ositelu to catalyst is in the range from 0.25 to 0.35 wt.%;

the amount of platinum is in the range from 0.2 to 0.3% by weight of catalyst and the amount of chlorine is in the range from 0.9 to 1.1% by weight of the catalyst; and

the catalyst additionally contains from 0.2 to 0.45 wt.% rhenium.

23. The catalyst prepared by the process comprising impregnation of the carrier for the catalyst according to item 12 with a catalytically effective amounts of platinum and chlorine.

24. The catalyst according to item 23, containing the carrier for the catalyst is impregnated with a catalytically effective amount of rhenium.

25. Method of reforming oil after Hydrotreating, comprising contacting the oil with the catalyst according to item 13 in the presence of hydrogen at elevated temperature and pressure.



 

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4 cl, 1 dwg, 1 tbl

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11 cl, 4 dwg, 3 tbl, 16 ex

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2 ex

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2 ex

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3 cl, 1 tbl, 7 ex

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2 cl, 7 tbl, 7 ex

The invention relates to a process for the isomerization of light paraffin hydrocarbons and can be used in refining and petrochemical industries

The invention relates to a process for the isomerization of light paraffin hydrocarbons and can be used in the refining and petrochemical industries

The invention relates to the refining and can be used for regeneration of the catalyst for reforming of gasoline fractions
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,-unsaturated aldehydes, method thereof and method of producing acrolein" target="_blank">

The invention relates to catalysts containing media, which caused the active phase on the basis of, in particular, molybdenum, Nickel, cobalt, bismuth, iron promoted with phosphorus and at least one alkali metal
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