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INVENTION
Russian Federation Patent RU2123514

Process for the preparation of gasoline, CATALYST FOR ITS IMPLEMENTATION

METHOD FOR PRODUCING MOTOR GASOLINE
AND CATALYST FOR CARRYING OUT

Name of the inventor: Kamensky AA .; Kosolapov AP .; Hairov VI .; Saakov E.M .; Nekrasov MS .; Derevtsov VI .; Mezherytskyi AM .; Nikitin VM .; Kalabin VB
The name of the patentee: Kamensky Anatoly
Address for correspondence:
Starting date of the patent: 1995.12.14

Use: Petrochemical industry. The inventive hydrocarbon fraction C 3 - C 4 - - C 4 containing 50-70% n-butene-1, no more than 1% of butadiene, else C 3 hydrocarbons are contacted with a catalyst containing 65 - 75 wt% of zeolite sverhvysokokremnezemnogo ZS. M-5 in the hydrogen form with the silicate modulus of 30-40, a degree of crystallinity of 80-100%, a residual content of sodium oxide, 0.01-0.1 wt.% zinc introduced therein in an amount of 1.8-2.2 wt. %, Based on catalyst and ion kremniyftor (SiF 6)2- in an amount of 0,25-3,75 wt.%, Based on catalyst and U-alumina and 100 wt.%. The process is carried out in fixed bed catalyst at 280-450 o C, pressure 0.3-1.0 MPa, volumetric feed flow rate of 500-1000 h -1. Fresh catalyst is activated by treatment with steam at 540-580 o C for 0.5 hours coked catalyst regeneration is carried nitrogen-air mixture with water vapor at a weight ratio of 2:. 1 to a residual coke content on the catalyst is 0.5-1.5 wt .% at 550-650 o C. The invention enables to simplify the process, to improve selectivity, activity, stability of the catalyst.

DESCRIPTION OF THE INVENTION

The invention relates to methods for preparing the catalyst of gasoline and for its implementation and can be used in the petrochemical industry.

For synthetic rubber divinyl manner after dehydrogenation of n-butane from a hydrocarbon mixture C 3 - C 4 or during CAT. krekitnga vacuum gasoil obtained butane-butylene fraction composition, wt%: n-butene-1-30-70;. divinyl C 4 H 6 0.3 - 1.0, hydrocarbons C 3 - C 4 - the rest up to 100%, which is used as domestic gas and has not qualified applications.

There is a method (Production of aromatic hydrocarbons from a liquefied petroleum gas process "Tsiklar" UOP Refining and Petrochemicals N 11, 1994, 3). Processing of C 3 liquefied gases - C 4 in benzene-toluene-xylene fraction (BTX fraction) containing, wt.%: benzene 22 - 27; Toluene 43 - 44; xylene 21 - 25; aromatic hydrocarbons C Sept. 2 - 3; C October 6 - 8, with a total yield of 61 - 6%. The "Tsiklar" (UOP Company, USA) carried out at 500 - 550 o C in a moving bed catalyst comprising: a zeolite ZS M-5, zinc and U - alumina. After separation by extraction with benzene get component of high-octane gasoline from 100 - 110 points on MM

The disadvantages of this method are the complexity of the hardware design process with a moving bed reactor, the low stability of the catalyst in a fixed bed in the processing of gases containing butylene and butadiene, and the inability to obtain and immediately automotive gasoline with RON 91 - 98.

The closest to the invention by the technical essence and attainable effect is a method comprising processing paraffin-olefinistyh hydrocarbon gaseous hydrocarbons C 3 - C 4 in the absence of hydrogen in a fluidized bed catalyst comprising gallium-containing zeolite Ga / ZSM-5 and U - alumina to yield of gasoline (US patent N 4851602, cl. the C 07 C 2/00, 1989).

The disadvantages of the method are the complexity of the application process, the low selectivity, catalyst activity and stability in the processing of gases containing butene and up to 1.0 wt.% Butadiene.

The purpose of the invention - production of high (without any additives octane) unleaded gasoline with RON 91 - 98.

This goal is achieved by a method of producing motor gasoline by contacting gaseous hydrocarbons C 3 - C 4 with a catalyst containing sverhvysokokremnezemny zeolite ZSM-5 and U - aluminum oxide, which uses a hydrocarbon fraction C 3 - C 4, containing 50 - 70 wt% of n. butene-1, no more than 1% by weight of butadiene, hydrocarbons, c 3 -. c -ostalnoe 4, using a catalyst comprising zeolite ZS M-5 in the hydrogen form with the silicate modulus of 30 - 40, the degree of crystallinity of 80 - 100%, a residual content sodium oxide, 0.01 - 0.1 wt% of zinc introduced therein in an amount of 0.25 -. 3.75 wt. %, Based on catalyst and ion kremniyftorid (SiF 6)2- in an amount of 0.25 - 3.75 wt% based on the catalyst, with the following component ratio, wt.%:. ZSM-5 zeolite described above - 65 - 75, U - aluminum oxide - to 100. The process is carried out in fixed bed catalyst at 280 - 450 o C, 0.3 - 1.0 MPa, volumetric feed flow rate of 500 - 1000 h -1, to supply fresh catalyst feed activated by treatment with steam at 540 - 580 o C for 0.5 hours Regeneration azotnovozdushnoy coked catalyst mixture is performed with water vapor at a weight ratio of 2:. 1 to a residual coke content on the catalyst is 0.5 - 1.5 wt% at 550. - 650 o C.

The goal is achieved and the catalyst to produce motor gasoline comprising metal-zeolite sverhvysokokremnezemny ZS M-5 and U - alumina in the hydrogen form with the silicate modulus of 30 - 40, the degree of crystallinity of 80 - 100%, a residual content of sodium oxide, 0.01 - 0 . 1 wt% of zinc introduced therein in an amount of 1.8 - 2.2 wt. %, Based on catalyst and ion kremniyftorid (SiF 6)2- in an amount of 0.25 - 3.75 wt% based on the catalyst, with the following component ratio, wt.%:. ZSM-5 zeolite described above - 65 - 75, U - aluminum oxide - 100.

Changing the composition of said catalyst activation and regeneration conditions leads to a decrease in its activity, selectivity and stability.

The catalyst is prepared by treating a zeolite sverhvysokokremnezemnogo HZS M-5 with a residual content of sodium oxide, 0.01 - 0.1 wt%, silicate module 30 -. 40 degrees of crystallinity and R = 80 - 100% for PPP 20% zinc nitrate solution with concentration of Zn (NO 3)2 5.3 weight% at a weight ratio zinc: zeolite 1:35 equivalent ratio Zn: NH 4 + (zeolite) 0.8 - 1.2, then kremniyftorida ammonium mixing the resulting mass. with aluminum hydroxide, boehmite and pseudoboehmite nature evaporation, molding, drying and calcination at 550 o C for 4 hours.

Example 1. 65 g of SIS-zeolite H-ZS M-5, CM = 30 and Na 2 O-0,01%, R = 80%, based on dry substance 20% IFR treated zinc nitrate 8.256 g of a mixer for 0, 5 -. 1.0 h and then dosed ammonium kremniyftorid 0.32 g, was stirred for 0.5 hours at 70 - 85 o C, whereupon the aluminum hydroxide cake IFR 70 - 80% in an amount of 32.95 g based on Al 2 o 3, the resultant mixture with stirring evaporated to PPP 55 - 60%, formed on the screw-press molding machine into extrudates of diameter 2 - 4 mm and a length of 4 - 9 mm, the extrudates were dried at 120 - 140 o C for 4 hours calcined at 550 o C for 4 hours.

The catalyst has a composition, in weight%: Zeolite H-ZS M-5-65,0, introduced into it with zinc 1,8;. kremniyftorid ion - 0.25; and U - Al 2 O 3 in an amount of 32.95, based on the catalyst.

Raw - butane-butylene fraction containing 0.5% butadiene, 50% n-butene-1, else C 3 hydrocarbons - C 4, is fed to the catalyst at 280 o C, 0.3 MPa, and the volume hourly space velocity of 500 h -1 after a preliminary activation (processing) by steam at 540 o C for 0.5 hours.

After the catalyst coking operation (time 30 days) at 8% coke Content conduct regeneration (burning coke) azotnovozdushnoy mixture with steam in a ratio of 2: 1 at 550 o C to a residual content of coke on the catalyst 1.5%, and then finish the regeneration and served again at the raw materials of the above parameters. After regeneration of the catalyst is completely recovers its original activity. Number of regeneration cycles - 24, the total life of the catalyst under these process parameters and regeneration - 2 years, ipso cycle - 30 days.

The results for the catalyst of Example 1 and the following examples are given in the table.

Example 2. 75 g of H-ZSM-5 zeolite ICS, CM = 40, Na 2 O 0,1% and R = 100% based on the dry substance is treated as in Example 1, which served 10.09 g of zinc nitrate, 4, 7 g of ammonium kremniyftorida and 19.05 g of aluminum hydroxide in an amount of cake to 19.05 g of Al 2 O 3.

The catalyst has a composition, in weight%: zeolite H-ZSM-5-75 with zinc introduced therein - 2.2;. kremniyftorid ion (SiF 6)2- -3.75; U - Al 2 O 3, -19.05; in an amount based on the catalyst.

Raw - butane-butylene fraction hydrocarbon C 3 - C 4 containing n-butene-1 - 70% 1% of butadiene, the remainder hydrocarbons C 3 -C 4 are contacted with said catalyst composition after the preliminary activation with steam at 580 o C in for 0.5 hours at 450 o C, 1 MPa, volumetric feed rate of 1000 h -1.

After coking (time 20 days) at a content of 12% coke catalyst mixture is regenerated azotnovozdushnoy steam at a weight ratio of 2: 1 at 650 o C to a residual coke content of 1.5%, after which the raw material is fed at 280 o C and operated at 450 o C, 1 MPa, volumetric feed rate of 1000 h -1. After multiple regenerations (18) the total period of service with these parameters - 1 year service cycle - 20 days.

Example 3. 70g CRS zeolite H-ZS M-5 CM = 35,0; Na 2 O 0,05% R (x-ray) = 90, based on dry substance of 20% with the SPT of Example 1 was treated with 9.17 g zinc nitrate salt, 2.5 g of ammonium kremniyftorida and 26 g of aluminum hydroxide in terms of Al 2 O 3.

. Composition of the catalyst: wt% HZSM-5 zeolite - 70,0 inserted therein with Zn 2.0; kremniyftorid ion (SiF 6)2 - 2.0; U - Al 2 O 3 - 26.0.

The process is carried on a catalyst composition on the said raw materials - hydrocarbon fraction of C 3 - C 4 containing 60% n-butene-1; 0.5% of butadiene, hydrocarbons, C 3 - C 4 - the rest at 365 o C, 0.65 MPa, and the volume hourly space velocity of 750 h -1. Before applying the raw material is treated with fresh catalyst (activated) steam at 560 o C for 0.5 h After coke on the catalyst achieve 10% azotnovozdushnoy subjected to regeneration with water vapor at a weight ratio of 2:. 1 to a residual coke content of 1% at 600 o C, and then again fed raw at 280 o C and working under the above parameters. The number of regenerations - 22, ipso catalyst cycle of 25 days. After regeneration, the catalyst restores its activity. The total catalyst life of 1.5 years.

Example 4 (for comparison). The catalyst is prepared according to Example 1, which is administered CRS zeolite, CM = 25, sodium oxide, 0,005%, R = 75 to 60 g on dry substance, 7.798 g of zinc nitrate, ammonium kremniyftorida 0.25 g and 38.1 g of aluminum hydroxide cake, based on Al 2 O 3.

. The catalyst composition: wt% Zeolite H-ZS M-5-60,0 introduced into it with zinc - 1.7; kremniyftorid ion 0.2; U - Al 2 O 3 - 38.1

Raw material contains 45% n-butene-1, 1.5% butadiene, C 3 -C 4 hydrocarbons - the rest, the catalyst is treated (activated) by steam at 520 o C for 1 hour, the process is carried out at 270 o C, 0 2 MPa, the feed space velocity 450 h -1. After the accumulation of coke on the catalyst regeneration is carried out 15% of the nitrogen-air mixture with steam in a weight ratio of 1: 1 to a residual content of 0.1% of the coke at 525 o C. The resulting catalyst cokes after 2 days of operation, after the regeneration does not restore the original activity .

Example 5 (for comparison). The catalyst is prepared according to Example 1, which take CRS zeolite H-ZS M-5, CM = 42, Na 2 O - 0,15%; R = 100% in an amount of 80 g on dry substance, 11.467 g of zinc nitrate, ammonium kremniyftorida 5.0 and 13.5 grams of aluminum hydroxide in terms of Al 2 O 3.

The catalyst composition by weight. %: Zeolite H-ZS M-5-80,0 with entered into it with zinc-2.5, kremniyftorid ion-4.0; U - - Al 2 O 3 -13.5.

The catalyst has a low mechanical strength. The catalyst was activated by steam at 590 o C for 0.5 hours. The process is carried out on the raw material composition according to Example 4, but with the contents of n-butene-1 = 75% at 460 o C, 1.2 MPa, feed space velocity 1100 h 1, after the accumulation of 7% of the coke is carried azotnovozdushnuyu regeneration with water vapor at a weight ratio of 3: 1 to a residual coke content of 2% at 700 o C. after the first regeneration, the catalyst loses its mechanical strength, crumble into powder, it does not restore its activity.

Example 6 (for comparison). The catalyst is prepared as in Example 1, activation of the catalyst with water vapor is not carried out, the process is conducted on raw material composition of Example 3 and under the conditions of Example 3. The catalyst was regenerated at a temperature azotnovozdushnoy mixture of Example 3, but the steam is not fed during regeneration, thus sharply regeneration temperature up to 850 - 1000 o C.

Coke is burned from the catalyst surface to 0.5%.

As a result, the catalyst loses its original activity after 5 days of operation, after running 3 days regenerations, the total lifetime of the catalyst - 3 months.

Thus, the proposed method allows cheap butanbutilenovoy fraction of synthetic rubber plants receive synthetic environmentally friendly high-octane motor gasoline AI 91-98 or high-octane component due to the reactions of oligomerization n-butene-1 with a conversion into oligomers by 75 - 90% with subsequent isomerization , cyclization to naphthenes, dehydrogenation of a monocyclic aromatic hydrocarbons with content of benzene catalyzate 1 - 3%, the amount of aromatic hydrocarbons 15 - 35%, olefins 15 - 28%, the rest - isoparaffins. Yield on raw gasoline 37.5 - 63.0% when the content of butene-1 in the feed of 50 - 70% and a liquid product selectivity of 75 - 90% of the content of n-butene-1.

Motor gasoline AI-91-98 have a high induction time to oxidation (950 - 1200 m) with the introduction of 0,01 o C0,05 wt% antioxidant additive "ionol."; without introducing additives - 450 min.

CLAIM

1. A method for motor gasoline by contacting gaseous hydrocarbons C 3 - C 4 with a catalyst comprising zeolite sverhvysokokremnezemny metal-ZS M-5 and U-alumina, characterized in that the hydrocarbon fraction C 3 - C 4, containing 50 - 70% n-butene-1, no more than 1% of butadiene, hydrocarbons, c 3 - c 4 - the rest, the catalyst comprising a zeolite ZS M-5 in the hydrogen form with the silicate modulus of 30 - 40, the degree of crystallinity of 80 - 100%, a residual oxide 0.01 sodium -. 0.1 wt% of zinc introduced therein in an amount of 1.8 - 2.2 wt%, based on catalyst and ion kremniyftorid (SiF 6)2- in an amount of 0.25 -. 3 . 75 wt% based on the catalyst at the following component ratio, wt.%:

Zeolite ZS M-5 - 65 - 75

U-alumina - Up to 100

the process is conducted in fixed bed catalyst at 280 - 420 o C, 0.3 - 1.0 MPa, volumetric feed flow rate of 500 - 1000 h -1, feed prior to feeding the fresh catalyst is activated by treatment with steam at 540 - 580 o C for 0.5 h and regeneration of the coked catalyst is carried nitrogen air mixture with steam at a weight ratio of 2: 1 to a residual coke content on the catalyst is 0.5 - 1.5 wt% at 550 - 650 o C..

2. A catalyst for producing gasoline automobile, comprising metal-zeolite sverhvysokokremnezemny ZS M-5 and U-alumina, characterized in that it comprises ZS M-5 zeolite in the hydrogen form with the silicate modulus of 30 - 40, the degree of crystallinity of 80 - 100% residual sodium oxide content of 0.01 - 0.1 wt% of zinc introduced therein in an amount of 1.8 -. 2.2 wt%, based on catalyst and ion kremniyftorid (SiF 6)2- in an amount of 0.25. . - 3.75 wt% based on the catalyst at the following component ratio, wt.%:

Zeolite ZS M-5 - 65 - 75

U alumina - Up to 100 \

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Publication date 07.04.2007gg