The method of preparation of the catalyst and method of isomerization of paraffin hydrocarbons with4-c7

 

(57) Abstract:

The invention relates to processes and catalysts for medium-temperature isomerization of hydrocarbons. The method of preparation of mordenite-containing catalyst by mixing the mordenite in the hydrogen or ammonium form, with a ratio of SiO2/Al2ABOUT3within 14-23, with inorganic binders, one or more kaleidograph acids or their ammonium salts (with 1 part of mordenite take 0,11-0,66 part of the binder and 0.003 to 0.15 of one or amounts kaleidograph acids or their ammonium salts based on the weight of the halogen). The resulting mixture was formed into granules media, which after drying is subjected to two treatments: in the drained gas containing less than 300 million-1about.h. moisture (air, nitrogen) at temperatures of 400-600°C in a medium containing at least 500 million-1about.h. moisture (steam-air mixture, combustion gases) at a temperature of 250 to 500°C. heat treated pellets carrier is impregnated with a solution of the precious metal compounds from the calculation of its introduction in the catalyst is 0.1-1% in the presence of hydrochloric and/or hydrofluoric acid, in the amount of 0.3-5% by weight of the carrier in the calculation of the halogen, and the ratio of the volume of impregnating rastvorenie 400-550°C. As a binder used alumina, clay, silica gel, hard-shelled land or mixtures thereof with alumina. The catalyst prepared by the proposed method, carry out the isomerization of paraffin hydrocarbons WITH4-C7in the presence of hydrogen at a temperature of 180 to 300°C, davlenie 1-5 MPa, the ratio of hydrogen : hydrocarbon 0,5-4, the volumetric feed rate of the raw material of 0.5-4 h-1. The catalyst increases the degree of isomerization and selectivity of the process. 2 N. and 9 C.p. f-crystals, 1 table.

The invention relates to processes and catalysts for the isomerization of paraffin hydrocarbons WITH4-C7.

In particular, the invention relates to a process and catalyst temperature isomerization carried out at temperatures of 150-350°C (240-300°C) in the presence of hydrogen on the catalysts containing crystalline aluminosilicates of the zeolite.

Specifically, the invention relates to the isomerization process in the presence of a mordenite-containing catalyst, which also contains a matrix (binder) and the metal of the 8th group. For isomerization generally used acid (hydrogen form of mordenite. With this purpose, the original sodium form is transferred to the AMM is 3442794).

Isomerization catalysts, except mordenite, contain a binder, typically aluminum oxide and a precious metal of the 8th group, typically platinum.

To improve the activity of mordenite-containing catalyst in the isomerization process conduct dealumination, i.e., the increase in molar relationship SiO2/Al2O3.

The ratio of SiO2/Al2O3in the original mordenite usually close 10. There is a method of increasing the activity of mordenite-containing isomerization catalyst by increase of this ratio to 19 (U.S. Pat. USA 4018711) and 20 (U.S. Pat. USA 3507931) by acid treatment of the original zeolite. Acid treatment leads to dissolution and removal of aluminum from the lattice of the zeolite and, accordingly, the increase in SiO2/Al2O3.

The best activity of the reaction of isomerization of pentane is achieved when the ratio of SiO2/Al2O3=17 (J. Cat. 66, 290. 1980.)

Heat treatment with water vapor, with subsequent acid treatment of the mordenite can improve the ratio of SiO2/Al2O335 (U.S. Pat. USA 3506400) and even up to 100 (U.S. Pat. USA 3551353).

However, increasing the ratio of SiO2/Al2O3to via with the destruction of the crystal lattice of the zeolite.

The closest to the technical essence of the present method is a method for the isomerization of a hydrocarbon at a temperature of 150 to 400°C, a pressure of 1-5 MPa, the ratio of hydrogen/feedstock from 0.5 to 4 and volume rate of feed of 1.5-4 h-1in the presence of isomerization catalyst, which is prepared as follows.

A. Treatment of acid mordenite at a temperature of 40-100°With the aim of increasing the ratio of SiO2/Al2ABOUT3to 15-22.

b. Processing of the received dealuminated mordenite steam-air mixture at temperatures of 300-600° with the purpose of separation of aluminum from the zeolite lattice to obtain the ratio of aluminum in the lattice/ extracted from lattice aluminum in the range 1-10.

C. a Mixture of mordenite with a refractory inorganic oxide with a ratio of the mordenite/oxide is from 1:1 to 99:1.

d. Application of a metal of group VIII on mordenite, oxide or their mixture.

E. calcining the catalyst at a temperature of 300-600°C.

f. Restore the specified catalyst with hydrogen at a temperature of 300-600°C. (U.S. Pat. USA 5264648 from 23.11.1993 - prototype).

Although the isomerization catalyst prepared in the above manner, and provides herasimovich fractions is not as effective.

Determining for octane product features isomerization is the concentration of isopentane in a mixture of pentane from (from5/ S5and the total content of the most high-octane isohexanol 2,2 and 2,3-dimethylbutanol in a mixture of hexanol (2,2 DMB+2,3 DMB)/1:6In%.

Index isomerization AI equal to

AI=[(from5/ S5)+(2,2 DMB+2,3 DMB)]×100%

Comparison of AI raw materials and product determines the growth of AI and characterizes the activity of the catalyst and the effectiveness of the isomerization process. The selectivity of the catalyst is also not high enough, a significant portion of raw materials 4-7% turns into gas.

Another disadvantage of this method prototype is associated with a complex procedure for preparation of the catalyst, in particular with vapor processing mordenite. Mordenite is a powder and pass through a layer of steam-air mixture requires special equipment, which is usually not available on catalyst factories.

The present invention is to develop a method of preparation of the catalyst with improved isomerization of light gasoline fractions by increasing the activity and selectivity of the catalyst is a zeolite, mostly mordenite, with a high ratio of SiO2/AlO3inorganic oxide binder and a precious metal of group VIII, including mixing the zeolite with a binder, applying the indicated mixture of precious metal, calcining and restore Katalizator hydrogen, and the catalyst is prepared as follows:

- mix the mordenite in the hydrogen or ammonium form, characterized by the ratio of SiO2/Al2O3within 14-23, inorganic binder, one or more kaleidograph acids or their ammonium salts, and 1 part of mordenite take 0,11-0,66 part of the binder and 0.003 to 0.15 of one or amounts kaleidograph acids or their ammonium salts based on the weight of the halogen.

the mixture is molded to obtain a pellet carrier, which after drying is subjected to two heat treatments:

in the drained gas containing less than 300 million-1about.h. moisture (air, nitrogen) at temperatures of 400-600°C.

- in a medium containing at least 500 million-1about.h. moisture (steam-air mixture, combustion gases) at a temperature of 250 to 500°C.

- heat treated pellets carrier is impregnated with a solution of the precious metal compounds based it in kaliwat in a stream of dry air at a temperature of 400-550°C.

As a binder is preferably used aluminum oxide. It is mixed with zeolite, usually in the form aluminum hydroxide which, after calcination of the carrier is converted into oxide. Instead of aluminum oxide or together with the use of other types of binding clay (kaolin, bentonite), silica gel, hard-shelled land.

As kaleidograph acids using hydrogen fluoride (hydrofluoric acid) and/or hydrochloric (hcl) or ammonium salts of these acids. Kaleidotrope acid is preferably introduced in a binder, such as alumina.

After heat treatments a large part of the fluorine remains in the catalyst, and chlorine, basically, is removed.

At the stage of mixing additional nitric acid in the amount of 0.003 to 0.03 parts per 1 part of mordenite per 100% HN3.

Preferably as a precious metal used platinum when its content in the catalyst 0,15-0,45%, and impregnation with a solution of metal is carried out in the presence of hydrochloric and/or hydrofluoric acid in the amount of 0.3-5% by weight of catalyst based on the halogen, the ratio of the volume of the impregnating solution to the weight of the carrier is 0.4 to 0.9 l/K is P CLASS="ptx2">Up to 20% of mordenite in the catalyst can be replaced by zeolite or zeolite-type pentasil, for example, ZSM-5.

Salient features of the proposed method are:

a mixture of mordenite with a ratio of SiO2/Al2ABOUT314-23 in the hydrogen or ammonium form with a binder in the presence of kaleidograph acid, preferably hydrofluoric or hydrochloric) and/or their ammonium salts. This can be used not only hydrogen form of mordenite, the resulting dealuminated acid (as in the known solution), but also high-modulus mordenite obtained by direct synthesis, hydrogen and ammonium forms (Chem. Abst. No. 132, No. 14, 2000, s.)

the number kaleidograph ammonium acids or their salts is from 0.003 to 0.5 part per 1 part of the mordenite in the calculation of the halogen.

- molded carrier after drying, subjected to 2 treatments, one of them in a stream of dried gas moisture content less than 300 million-1about.h. (air, nitrogen) at a temperature of 400-600°C, and the other in a medium containing at least 500 million-1about.h. moisture (steam-air mixture, combustion gases) at a temperature of 250 to 500°C.

after vysokosernistykh acids.

the catalyst was calcined in a stream of dry air at a temperature of 400-550°.

The result is a catalyst, which in the known process conditions for the isomerization of pentane-hexane fraction get a stable product with index isomerization (AI) for 3-5 higher than in the known method on the same raw materials. This means that the octane isomerate under the same test conditions will be higher by 1-3 p.

The yield stable isomerate WITH+5characterizing the selectivity of the process, is extremely high and is 96% and above in the calculation of the content of C5+in raw materials. In the specified catalyst can be known additive elements, improves the activity of the isomerization catalyst, such as zirconium (E. R. 0253743), the rare earth Lemetti lanthanum, cerium (A. C. the USSR 1324149). However, the catalyst activity is so high that their presence is optional.

The catalyst contains impurities that are usually present in the mordenite, such as sodium, magnesium in the number of tenths of a percent.

The object of the present invention is also a method for the isomerization of paraffin hydrocarbons on the catalyst, cocoa catalyst of the following examples:

Example 1

For the preparation of isomerization catalyst used mordenite with a ratio of SiO2/Al2O3=20, which was obtained by dealuminated mordenite with a ratio of SiO2/Al2O3=12 acid.

The pellet of aluminum hydroxide containing 24% Al2ABOUT3(loss on ignition at 550°With 76%) are thoroughly mixed with solutions of hydrofluoric and then hydrochloric acid. The resulting mixture is mixed with a powder of the above mordenite. 1 weight.h. mordenite take 0,19 h aluminum oxide, 0,020 h, fluorine, 0,013 h of chlorine in the form of acids.

Under stirring to evaporate the moisture, and then the mixture was added 60% nitric acid in a quantity of 0.8 cm3100 g of calcined carrier. This corresponds 0,0087 century including NH31 century including mordenite.

After further mixing, the mass is formed into obtaining extrudates with a diameter of about 2 mm extrudates, dried at 130°C and calcined in a stream of dry air (less than 300 million-1about. moisture) at a temperature of 530°C, then reduce the temperature to 400°C and treated at this temperature, the vapor mixture containing about 15%.h. water vapor for 4 hours.

Those who account application 0,35% Pt on the weight of the catalyst. In the impregnating solution further add hydrochloric acid in an amount corresponding to 1% chlorine by weight of the catalyst. The total amount of impregnating solution of 0.8 l/kg media.

The catalyst was dried (100-130°C) and then calcined in a stream of dry air at 500°C.

The catalyst was tested at pilot plant with circulating hydrogen-containing gas.

Test conditions: a pressure of 2.5 MPa, the volumetric feed rate of 1.5 h-1the ratio of circulation of hydrogen 580 nl/l of raw materials, temperature, 250°C. Before use, the catalyst is reactivated by hydrogen at 450°C. the raw material used hydrotreated pentane-hexane fraction. Index isomerization of raw materials (IMS) is to 30.5%. The formula for calculating the AI is given in the description.

Index isomerization catalyzate 77,1%, the Yield of hydrocarbons FROM5+from their content in the raw material is 98%.

Basic data on the method of preparation of the catalyst and the test results hereinafter are given in the table.

Example 2

The catalyst is prepared in a similar way to example 1 with the following differences.

One part of mordenite take 0,11 including aluminum oxide, 0,003 including fluorine, chlorine is not added. Temperature which is 72%, the release of hydrocarbons FROM5+of 99.1%. The example illustrates the performance of the isomerization catalyst with a lower limit of the ratio of the aluminum oxide: the mordenite and the halogen/mordenite at the stage of mixing.

Example 3

The catalyst prepared according to example 1 with the following differences:

The heat medium in the presence of dry air is carried out at 400°C and humidified air (2% vol. moisture) at 500°C (2 hours), the catalyst was tested under the conditions and raw materials of example 1.

AI was 72.2%, the yield of hydrocarbons FROM5+99,2%. The example illustrates the upper limit of the heat treatment temperature of the medium moist air.

Example 4

The catalyst prepared according to example 1 with the following differences.

The heat carrier in a dehumidified air is carried out at 600°C and humidified air at a temperature of 250°C (6 hours).

When tested under the conditions of example 1 index isomerization (AI) is 71.2%, exit C5+99,2%.

The example illustrates the boundary limits of the temperature of thermal carrier drained and wet gases.

Example 5

The method of preparation of catalyst a similar set forth in example 1 with the following the de hydrofluoric acid of 0.15 PM 1 hour of mordenite. In addition, the catalyst is calcined at a temperature of 550°C.

When tested under the conditions of example 1 AI 69,0% yield WITH5+of 97.8%.

The example illustrates a maximum ratio of binder/mordenite.

Example 6

The catalyst is prepared analogously to example 1 with the difference that the use of mordenite in the hydrogen form with a ratio of SiO2/Al2O3=14. In addition, the processing vapor mixture is conducted at a temperature of 350°C, and a vapor mixture contains 45% of water vapor. When the condition test specified in example 1, AI is 69.3% and5+98,0%. The example illustrates the lower limit of the ratio of SiO2/Al2O3that can be applied to obtain a catalyst.

Example 7

The catalyst prepared according to example 1 with the difference that the use of mordenite in the hydrogen form with a ratio of SiO2/Al2O3=23. The catalyst activity under the conditions of test described in example 2 corresponds to AI 70.1% of the output WITH5+97,5%. The example illustrates the upper limit of SiO2/Al2O3in mordenite, suitable for preparation of the catalyst according to the present UB>2/Al2O3=17. The zeolite obtained by direct synthesis. The catalyst is prepared analogously to example 1, but the processing wet gas is conducted for 7 hours when the moisture content in the air of 1.5% vol.

The catalyst is used under the conditions of example 1 at a temperature of 250° and an additional 260°.

At a temperature of 250°AI equal 73,0%, and the output FROM5+98,7%, at a temperature of 260°AI 79,1%, and the output FROM5+96,7%.

Example 9 (comparative)

The catalyst is prepared with NH4-mordenite, as in example 8, but not spend processing media humid air. At a temperature of 250°AI 65,3, exit C5+98,7%, at a temperature of 260°With AI equal to 70.5%, and exit WITH5+97,3%.

The example illustrates the positive effect of processing media wet gas. Without treatment close AI is achieved at temperatures of 10-15°C above.

Example 10 (comparative)

The catalyst with the use of NH4-mordenite with SiO2/Al2O3=17 prepared analogously to example 8, but without the introduction of Halogens at the stage of mixing.

When tested under the conditions of example 1 but at a temperature of 260°AI is 59,0%, exit C5+99,0%. Comparison of examples 10 and 8 illustrates the necessity of ardenica in the protonated form and the ratio of SiO2/Al2O3=20. The preparation method similar to example 1, with the difference that at the stage of mixing the injected hydrochloric acid in the amount 0,021 including chlorine for 1 h mordenite (fluorine do not enter). When tested under the conditions of example 1 AI is 72,0%, exit C5+96,7%.

Example 12

The catalyst prepared according to example 1 with the difference that instead of hydrofluoric and hydrochloric acids used ammonium salts of these acids. The results of the tests of the catalyst under the conditions of example 1: AI is equal to 76,8%, exit C5+97,7%.

Example 13

The catalyst prepared according to example 1 with the difference that hydrofluoric and hydrochloric acid is introduced into a mixture of mordenite and aluminium hydroxide. The results of the tests of the catalyst under the conditions of example 1 AI equal to 75.8%, exit C5+98,3%.

Example 14

For the preparation of the catalyst used NH4form of mordenite with a ratio of SiO2/Al2O3=17. The catalyst is prepared analogously to example 8, but additionally contribute 2% of fluoride during the impregnation of the carrier platinochloride acid. With this purpose, the heat-treated carrier is impregnated with a solution containing platygastroidea acid based Vvedenie% fluorine. Testing of the catalyst under the conditions shown in example 1, showed that AI is equal to 75.6%, exit C5+96,3%.

Example 15 (comparative)

The powder of the mordenite in the H form with ratios of SiO2/Al2O3=17 process vapor mixture containing 45% water vapor at a temperature of 350°C for 4 hours. Next, prepare the catalyst analogously to example 10 with the difference that the medium is not subjected to treatment with water vapor. The catalyst was tested under the conditions of example 1, AI is 67.2 per cent, exit C5+95,0%.

The example shows that the above-mentioned known method of preparation of the catalyst gives the worst results on activity than suggested.

Example 16

The catalyst is prepared analogously to example 1 with the difference that instead of the aluminum hydroxide used bentonite clay. The test results catalyst AI 72,0%, exit C5+96,3%.

The example illustrates the possibility of using other binders, as not only aluminum oxide.

Example 17

The catalyst prepared according to example 1 with the difference that the heat carrier is carried out in reverse order, beginning at 400°With wet gas, and then PR is P CLASS="ptx2">The example illustrates the possibility of conducting treatments in reverse order.

Example 18

The catalyst is prepared analogously to example 1 with the difference that 20% of mordenite replace 10% zeolite and 10% zeolite DCM (similar to ZSM-5). The catalyst was tested as in example 1. AI is 77.8%, the output of C5+95,8%.

The example illustrates the upper limit of the substitution of mordenite other zeolites.

Example 19

The catalyst is prepared analogously to example 11 with the difference that the carrier impregnated catalyst is a platinum compound is carried out in the presence of two acids, hydrochloric rate of 1% chlorine by weight of the catalyst and hydrofluoric from the calculation of the 3.5% fluorine by weight of the catalyst.

The catalyst was tested under the conditions of example 1. AI is 77.2 percent, entrance C+595,2%

Example 20

The catalyst prepared according to example 1, conduct the isomerization feedstock, the composition of which is given below.

The isomerization conditions: a pressure of 2.5 MPa, the ratio of hydrogen/feedstock 300 about/about (H2/SN,2), temperature 280°C, the volumetric feed rate of 2.5 h-1.The results of the test: AI=83, the output of C+597,5%.

PDEN above.

The test conditions: pressure of 1.5 MPa, the ratio of hydrogen/feedstock 700 about/about (N2/CH2,6), temperature 240°C, the volumetric feed rate of 0.8 h-1.

The results of the test: AI=80, exit WITH+598,3%.

Examples 20 and 21 illustrate a method of isomerization on the catalyst.

1. The method of preparation of the catalyst for isomerization of paraffin hydrocarbons, C4-C7containing mordenite with an increased ratio of SiO2/Al2ABOUT3inorganic oxide binder and the precious metal of the 8th group comprising a mixture of mordenite with a binder, the coating obtained on the medium compounds of precious metal, the annealing of catalysator and restore it with hydrogen gas at elevated temperatures, characterized in that the catalyst is prepared as follows: mix the mordenite in the hydrogen or ammonium form, characterized by the ratio of SiO2/Al2ABOUT3within 14-23, inorganic binder, one or more kaleidograph acids or their ammonium salts, and 1 hour of mordenite take 0,11-0,66 including a binder and 0.003 to 0.15 of one or amounts kaleidograph Ki is after drying is subjected to two treatments: in the drained gas, containing less than 300 million-1about.h. moisture (air, nitrogen) at temperatures of 400-600°C in a medium containing at least 500 million-1about. moisture (steam-air mixture, combustion gases) at a temperature of 250 to 500°C, heat treated pellets carrier is impregnated with a solution of the precious metal compounds from the calculation of its introduction in the catalyst is 0.1-1% in the presence of one or more acids, the dried catalyst was calcined in a stream of dry air containing less than 300 million-1moisture at a temperature of 400-550°C.

2. The method of preparation of the catalyst under item 1, characterized in that the binder used aluminum oxide.

3. The method of preparation of the catalyst under item 1, characterized in that the binder used clay (bentonite, kaolin, silica gel, hard-shelled land or mixtures thereof with alumina.

4. The method of preparation of the catalyst under item 1, characterized in that at the stage of mixing as kaleidograph acids using hydrogen fluoride (hydrofluoric acid) and/or muriatic (hydrochloric) or ammonium salts of these acids.

5. The method of preparation of the catalyst under item 1, characterized in that at the stage of mixing the additional use of nitric chotoviny catalyst under item 1, characterized in that the precious metal is used platinum content in the catalyst 0,15-0,45%.

7. The method of preparation of the catalyst under item 1, characterized in that the impregnation of the support with a solution of a precious metal compounds is carried out in the presence of hydrochloric (hcl) and/or hydrofluoric (HF) acid, in the amount of 0.3-5% by weight of the carrier in the calculation of the halogen.

8. The method of preparation of the catalyst under item 1, characterized in that the ratio of the volume of impregnating solution to the mass media is 0.4 to 0.9 l/kg

9. The method of preparation of the catalyst under item 1, characterized in that up to 20% by weight of mordenite replace-zeolite and/or zeolite type pentasil.

10. The method of preparation of the catalyst under item 1, characterized in that galoidvodorodnykh acid at the stage of preparation of the carrier is introduced into a binder, such as alumina.

11. Method of isomerization of paraffin hydrocarbons, C4-C7in the presence of hydrogen at a temperature of 180 to 300°C, davlenie 1-5 MPa, the ratio of hydrogen: hydrocarbon 0,5-4, the volumetric feed rate of the raw material of 0.5-4 h-1, characterized in that it is carried out on the catalyst prepared by any of the

 

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