The catalyst for dehydrogenization c2-c5-paraffins and how dehydrogenization c2-c5-paraffins

 

(57) Abstract:

Usage: in the refining process dehydrogenization paraffins. The inventive catalyst contains platinum 0.2 to 1.0 wt% tin, 0.02 to 1.0 wt% of chlorine to 0.02 - 0.05 wt% (Cl-and the rest of the media - titanium - silicalite or aluminum titanate, or silicon titanate with a titanium content of 0.2 - 2.5 wt%. This catalyst are dehydrogenization C2-C5-paraffins at a temperature of 500 to 700°C., a pressure of 1 - 2 kg/cm2and when flow rate 100-10000 h-1. 2 C. C.p. f-crystals, 2 tab.

The invention relates to catalytic compositions for dehydrogenization2-WITH5paraffins (i.e., paraffins, containing the number of carbon atoms in its molecule in the range from 2 to 5) to obtain olefins.

The increase in the demand for olefins to obtain certain chemicals (such as, for example, high-octane gasoline, synthetic resins, pharmaceutical products and the like) gives dehydrogenization paraffins, more and more significant role from a commercial point of view.

In this context, from a commercial point of view, a particularly interesting process is the hydrogenation of light paraffins is emer: production of gasoline, processes for the alkylation of aromatic hydrocarbons, the conversion of aromatic hydrocarbons, the production of isobutylene to MTBE and so on).

For processes of this type have been used on an industrial level, it is necessary for the conversion of paraffins was held in high degree and, above all, to paraffins are selectively was hydrogenations in olefins, and any adverse reactions should be minimized.

Indeed, it was published several patents, in which he described dehydrogenate paraffins using noble metals deposited on some media, such as-Al2O3, SiO2the oxides of magnesium and to which was added alkali or alkaline earth metals .

The disadvantages of these systems was reflected in their low activity and selectivity and poor stability over time.

Improvements have also been made at the suggestion of other catalysts consisting of platinum in the presence of tin.

However, the catalysts known from the proposed technical solutions are not completely satisfactory from all points of view, i.e., the activity shown in the process of dehydrogenization linear paraffins, the selectivity relative to toadie time was found, what if Titan to add to the known catalytic media used in conjunction with catalysts containing platinum and tin, can be obtained by catalytic composition, which shows higher values of selectivity and activity in the processes of dehydrogenization paraffin to olefin production.

The catalytic composition in accordance with the present invention for dehydrogenization2-C5differs in that it contains platinum in a quantity in the range from 0.01 to 3% by weight, if necessary, tin number, in the range of 0 to 1.5 mass media selected from: titanate, aluminum oxide, titanate oxide of silicon and/or titanium-silicalite, in which the amount of titanium in the media is in the range from 0.05 to 3% by weight and preferably ranges from 1% to 2% by mass.

Titanium-silicate is a synthetic zeolite, in the crystal lattice which silicon is partially replaced by titanium.

Named zeolite and method of its preparation is described in UK patent N 2.071.071.

Another aim of the invention consists in the process of dehydrogenization2-C5paraffins.

aboutWith, under pressure, in the range from 1 to 2 kg/cm2(98-196 kPa) and flow rate GHSV, estimated according to the flow of gaseous paraffins, fed to the reactor being in the range of 100-10000 h-1.

P R I m e R 1. A sample of titanium-silicate with a particle size smaller than 30 (μm), prepared in accordance with the process described in example 1 of the patent in the UK N 2071071, was impregnated with a solution, acidified with HCl, containing hexachloroplatinic acid and containing the dihydrate douglasthe tin, using the following procedure:

of 1.16 g of SnCl22H2O was dissolved in 8.6 cm3concentrated hydrochloric acid was added 4,07 g (2.5 cm3) aqueous solution hexachloroplatinic acid (containing 25% by weight of Pt).

The volume of solution was diluted to the General solution in 60 cm3and received Rast thief was slowly added to the titanium-silicalite.

After impregnation, the resulting material was concentrated by drying at a temperature of approximately 120aboutWith over priblizitel is) equal to 500 h-1for about 2 hours

Whether the product is subsequently recovered in the flow of H2/N2(molar ratio of 1) at 600aboutWith that flowed with a bulk velocity (GHSV) equal to 500 h-1within approximately 2 hours

Finally got the catalyst, which had a chemical composition: 1% by weight Pt: 0.6% by mass of Sn 0.02 mass% Cl-98,38 by weight titanium-silicalite (0,2% by weight of Ti).

The catalyst was tested in the hydrogenation of propane in the reactor fluidized layer in the process at a temperature of 590about, a pressure of 1 kg/cm2(98 kPa) and flow rate (GHSV) 400 h-1moreover , the catalytic layer was obtained by dilution of the catalyst is aluminum oxide with a ratio of the catalyst to the alumina equal to 0.06 mass.

The results are shown in table.1 and 2.

P R I m m e R 2 (comparative). A sample of 100 g silicalite on grain size less than 30 microns with an average size of the crystals are in the range of 20-26 μm was impregnated SnCl22H2O and hexachloroplatinic acid in the solution was acidified with hydrochloric acid, and were used, such amounts, to get at the end of the catalyst, which had abotu scheme impregnation, drying, calcination and recovery was performed as described in example 1. The catalyst was finally tested in accordance with the procedure described in example 1, the reaction of dehydrogenization propane.

The results obtained are shown in table.1.

P R I m e R 3. A sample of 100 g microspherical alumina, prepared in accordance with the previously known technical solution, with grain size lower than 30 μm, with an area of 250 m2/g and a total porosity of 0.8 cm3/g was impregnated with an alcoholic solution obtained by dissolving 7.2 g of tetraethylorthosilicate 70 cm3ethyl alcohol in accordance with the following procedure; 100 g of aluminum oxide were placed in a quartz reactor placed inside the heating furnace.

The bottom end called quartz reactor through a distributor filed nitrogen with such velocity to be within the reactor, the linear speed of about 2 m/s, which causes fluidization material. With the upper end of the reactor drip method was added to the alcohol solution of Ti(OC2H5)4- obtained by dissolving 7.2 g of tetraethylorthosilicate 70 cm3ethyl alcohol - and material constantly support the l was heated to 500aboutC. Upon reaching this temperature, the continued flow of nitrogen and the material was caliciviral in the air stream for 2 hours

The product obtained after calcination at 550aboutWith containing 2.5% by weight of TiO2that was soaked with a solution, acidified with HCl, containing suitable quantities of SnCl22H2O and H2PtClb, so that in the end to obtain a product containing: 1 weight% Pt and 0.6 by weight Sn; 2,45% by weight of TiO; 0.02 mass% Cl-; 95,93% by weight of Al2O3.

The scheme impregnation and activation were performed as already described in the previous examples.

Finally the catalyst was tested for dehydrogenization propane in accordance with the scheme of example 1. The results are shown in table.1.

P R I m e R 4 (comparative). Sample microspherical alumina, prepared in accordance with the previously known technical solution, with particle size less than 30 μm, a surface area of 250 cm2/g and a total porosity of 0.3 cm3/g, was impregnated with the solution was acidified with hydrochloric acid containing hexachloroplatinic acid and dehydrate douglasthe tin, in accordance with the following procedure:

of 1.16 g of SnCl22H2The/SUP>) aqueous solution hexachloroplatinic acid (25% by weight).

The volume of solution was diluted to a total volume of 80 cm3and the resulting solution was slowly added to 100 g of alumina.

At the end of the impregnation, the material was concentrated by drying, calcining and recovery in the same conditions as already described in example 1.

Got the catalyst following chemical composition: 1% by weight of Pt and 0.6% by weight of Sn 0.02 mass% Cl-98,38% by weight of Al2O3.

The catalyst was tested by dehydrogenization propane in the fluidized catalyst layer according to the procedure of example 1.

The results are shown in table. 1 and 2.

P R I m e R 5. (comparative). A sample of the same aluminum oxide as used in example 4 was mixed with calcium oxide when using esters of silicic acid in accordance with the following procedure.

100 g of aluminum oxide were loaded in a quartz reactor placed in a heating furnace. The bottom end called quartz reactor through a distributor filed nitrogen with such velocity to be within the reactor, the linear speed of about 2 m/s, which causes fluidization materialstesting 34 g orthosilicate 43 cm3ethyl alcohol - and material is constantly maintained at room temperature. After adding the material started to heat up and gradually the material was heated up to 550aboutC. Upon reaching this temperature, the continued flow of nitrogen and the material was caliciviral in the air stream for 2 hours

The resulting product had the following chemical composition: 11.5% by weight of SiO2; and 88.5% by weight of Al2O3with a surface area of 245 m2/g and a total porosity of 0.7 cm3/,

This material was impregnated with the same number, which were used in example 1, SnCl22H2O and hexachloroplatinic acid by the same procedure, which is already known for the preparation of the catalyst.

The catalyst was tested for hydrogenation of propane in accordance with the scheme described in example 1.

The results obtained are presented in table. 1.

P R I m e R 6. 100 g of silicon oxide with a grain size less than 30 microns, a surface area of 250 cm2/g and a total porosity of 0.6 cm3/g were impregnated with an alcoholic solution obtained by dissolving 7.2 g of tetraethylorthosilicate 53 cm3ethyl alcohol using the same procedure Kweli solution acidified with hydrochloric acid and containing a suitable amount of SnCl22H2O and H2PtCl6to get in the end product containing 1% by weight Pt: 0.6% by mass of Sn 2,45% by weight of TiO2and 95,93% by weight of Al2O3and 0.01% by weight of CL-.

Scheme implementation impregnation and activation was the same as that described in the previous examples.

In the end, the catalyst was tested for dehydrogenization propane in accordance with the scheme set forth in example 1.

The results obtained are presented in table. 1.

P R I m e R 7. (comparative) 100 g of silica with a particle size less than 30 microns, a surface area of 250 m2/g and a total porosity of 0.6 cm3/g were impregnated with an aqueous solution, acidified with perchloric acid containing SnCl22H2O and hexachloroplatinum acid (in the same quantities as in example 1), then the impregnated silica was subjected to drying, calcining and recovery in accordance with the same procedure as described in example 1.

The result was the catalyst having the following chemical composition: 1% by weight of Pt and 0.6% by weight of Sn 0.02 mass% Cl-; 98,38% by mass is concateno tested for dehydrogenization propane under the same conditions, what is described in example 1.

The results obtained are shown in table. 1.

1.The catalyst for dehydrogenization2- C5-paraffins containing platinum, tin, chlorine and media, wherein the media contains from titanium-silicalite, or titanate, aluminum oxide, or a titanate oxide of silicon with titanium content of 0.2 - 2.5 wt.%, in the following, wt.%:

Platinum 0,2 - 1,0

Tin 0,02 - 1,0

Chlorine 0,02 - 0,05

The media and the Rest

2.How dehydrogenization2- C5-paraffins by entering them at a temperature of 500 to 700oC and a pressure of 1 - 2 kg/cm3into the reactor containing the catalyst containing platinum, tin and chlorine on the carrier, characterized in that the use of a catalyst containing as a carrier of titanium-silicate or titanate, aluminum oxide, or a titanate oxide of silicon with titanium content of 0.2 - 2.5 wt.%, in the following ratio of components in the catalyst, wt.%:

Platinum 0,2 - 1,0

Tin 0,02 - 1,0

Chlorine 0,02 - 0,05

The media and the Rest

and the process is carried out at flow rate 100 - 1000 h-1.

 

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9 cl, 4 tbl, 1 dwg, 4 ex

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35 cl, 10 tbl, 84 ex

FIELD: chemistry.

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10 cl, 2 dwg, 1 tbl, 6 ex

FIELD: chemistry.

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3 cl, 1 tbl, 14 ex

FIELD: chemistry.

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EFFECT: reduced ill effects of air contamination caused by by-products of incomplete high-temperature combustion of organic substances.

21 cl, 34 ex, 4 tbl

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