Catalyst for steam reforming of naphtha and refinery gases

 

(57) Abstract:

The invention: is to create a catalyst for steam reforming of hydrocarbons having the following composition, wt. Nickel oxide 0,3 8,0; aluminum oxide 0,65 1,80; magnesium oxide 0,45 - 1,65; calcium oxide 0,35 1,40; potassium oxide 0,75 3,35; media else. 1 C. p. F.-ly, 2 tab.

The invention relates to the production of catalysts for steam reforming of heavy hydrocarbon gases and liquid hydrocarbons including naphtha to produce hydrogen, azotobacteraceae mixture and process gases in the chemical and petrochemical industries.

Known catalyst for steam reforming of hydrocarbons containing, by weight. 8,0-14,0 NiO; 3,4-8,0 Al2O3on the media containing, by weight. of 0.12 to 0.80 Cao, 0.06 To 0,23 MgO; 0,08-0,71 Na2O; 0,32-2,85 SiO2; -Al2O3rest [1]

The main disadvantage of the catalyst is low coxologist. In steam reforming of liquid hydrocarbons he quickly sakakawea and destroyed.

The closest solution to the technical essence and the achieved effect is the catalyst for steam reforming of liquid hydrocarbons (gasoline direct race) containing, by weight. 8,0-12,0 NiO; 1,0-3,8 Al2OThe catalyst is prepared by impregnation of the carrier of the composition based on alumina, with an aqueous solution of nitrate salts of Nickel, aluminum, magnesium and lanthanum with subsequent annealing at 600about[2]

The disadvantage of the catalyst is low coxologist at high contact loads. When steam reforming of gasoline on the catalyst with a volume velocity of 2.0 1/h and above there is a continuous increase of the coke deposits with a rate of 0.06 g/l cat. per hour [2] associated with a decrease in selectivity of the catalyst under these conditions; as a result of reaching the critical content of coke (4-6 wt.) the catalyst starts to break down.

Steam reforming of liquid hydrocarbons in industrial conditions is carried out at a temperature of the entrance to the catalyst bed 400-450aboutC, molar ratio of N2O/C3,5-3,8 and flow rate of liquid raw materials 0,8-1,1 1/h

Under these conditions, the Nickel catalysts are susceptible to coking, and at a temperature below 500aboutWith gasification of coke by steam from the reaction C+ H2O __ CO+H2occurs at a rate an order of magnitude smaller than the formation of carbon by cracking liquid hydrocarbon, CnHm___n C+ m/2 H2< / BR>
With increasing moviesa.

For carrying out steam reforming of liquid hydrocarbons, including naphtha with a high content of aromatics, without kokoulina required suppression kekirawa properties of Nickel catalysts with simultaneous acceleration of gasification of coke with the active component of catalysts. This promotion effect can be achieved by use as promoters of oxides of alkali and alkaline earth metals having a high basicity (MgO, CaO) and suppressing the adsorption and cracking of hydrocarbons (K2About). To reduce entrainment of potassium water vapor is applied media containing kaolin.

The combined use of these oxides for the promotion of the active component of Nickel catalysts reduces kokoulina and allows to achieve the optimal combination kekirawa and the gasification of the functions of the active component by increasing the degree of carbonation in the conditions of steam reforming.

The invention consists in creating a catalyst for steam reforming of liquid hydrocarbons, including naphtha, applied with an active component comprising addition of aluminum oxide and magnesium oxide calcium, potassium carrier based on alumina or ACS is I 3,0-8,0

Aluminum oxide 0,65-1,80

Magnesium oxide 0,45-1,65

Calcium oxide 0,35-1,40

The potassium oxide 0,75-3,35

The media and the Rest

In contrast to the catalyst of the prototype during steam reforming of hydrocarbons containing up to 15 wt. the aromatics on the proposed catalyst is not kokoouline and at loads up to 4 1/h of liquid raw materials and reduced to 2.5 relationship of H2O/C it maintains high stability.

P R I m e R 1. To prepare 1000 g of the catalyst at 903 media ( -Al2O3) with a porosity of 0.32 cm3/g for two impregnation with an aqueous solution, is applied 233,6 g of Nickel nitrate setevogo Ni(NO3)26N2On (60,0 g NiO); for 77.3 g of aluminum nitrate deviational Al(NO3)39H2O (10,5 g Al2O3); 31.6 calcium nitrate chetyrehletnego CA(NO3)24H2About (7.5 g Cao), 44,5 g of magnesium nitrate setevogo Mg(NO3)26N2On (7,0 MgO) and 25.8 g of potassium nitrate anhydrous KNO3(12.0 g2O).

After each impregnation the catalyst is dried and calcined at 450aboutWith no less than 4 hours Get a catalyst of the following composition, wt.

Nickel oxide 6,0

Aluminum oxide 1,05

Magnesium oxide 0,70
2
O3with a content of 8 wt. kaolin) with a porosity of 0.25 cm3/g for four impregnation aqueous solution is applied 311,4 Nickel nitrate setevogo Ni(NO3)26H2O (80,0 g NiO); 132,5 g of aluminum nitrate deviational Al(NO3)3N2On (18.0 g Al2O3); 59.0 g of calcium nitrate chetyrehletnego Ca(NO3)24H2O (14.0 g Cao); 105,0 g of magnesium nitrate setevogo Mg(NO3)26H2O (16.5 g MgO) and to 71.9 g of potassium nitrate anhydrous KNO3(33,5 g2O).

After each impregnation the catalyst is dried and calcined at 450aboutWith no less than 4 hours Get a catalyst of the following composition, wt.

Nickel oxide 8,0

Aluminum oxide 1,80

Magnesium oxide 1,65

Calcium oxide 1,40

The potassium oxide 3,35

The media and the Rest

P R I m e R 3. To prepare 1000 g of catalyst on 868,0 g ceramic media ( -Al2O3with a content of 4 wt. kaolin) with a porosity of 0.25 cm3/g for four impregnation aqueous solution is applied 272,5 g of Nickel nitrate setevogo Ni(NO3)26H2O (70,0 NiO); 110,4 aluminum nitrate deviational Al(NO3)39H2O (15.0 g of Al2O3); 463 g of calcium nitrate is26N2On (13,0 g MgO) and 25, 8 g of potassium nitrate anhydrous KNO3(23,0 g2O).

After each impregnation the catalyst is dried and calcined at 450aboutWith no less than 4 hours Get a catalyst of the following composition, wt.

Nickel oxide 7,0

Aluminum oxide 1,50

Magnesium oxide 1,30

Calcium oxide 1,10

The potassium oxide 2,30

The media and the Rest

P R I m e R 4. To prepare 1000 g of catalyst on 94,8 g ceramic media ( -Al2O3with a content of 2 wt. kaolin) with a porosity of 0.25 cm3/g for three impregnation aqueous solution is applied of 116.8 g of Nickel nitrate setevogo Ni(NO3)26N2On (30.0 g NiO); 47.8 aluminum nitrate deviational Al(NO3)3N2About (6.5 g Al2O3); of 14.7 g of calcium nitrate chetyrehletnego CA(NO3)24H2About (3.5 g Cao); 28.6 g of magnesium nitrate setevogo Mg(NO3)26H2O (4.5 g MgO) and 16.1 g of potassium nitrate anhydrous KNO3(7.5 g2O).

After each impregnation the catalyst is dried and calcined at 450aboutWith no less than 4 hours Get a catalyst of the following composition, wt.

Nickel oxide 3,0

Aluminum oxide 0,65

Magnesium oxide 0,45

Oxide Kalam.1.

P R I m e R 5. For testing coxologist proposed catalysts in steam reforming of liquid hydrocarbons used as raw material mixture of normal hexane to benzene containing 15% benzene in maxogenol close to nafta. The reforming is carried out at 500aboutWith a molar ratio of N2O/C=2.5 and atmospheric pressure in the installation of a flow-through microreactor at contact load 4,0 1/h, liquid raw materials.

Download 6.0 cm of catalyst (fraction of 1.0-1.6 mm). Activation of the catalyst is carried out with hydrogen (0.2 mol/cm3cat.h) at 550aboutC for 2 hours the composition of the gas reforming analyze chromatography. Duration of test 4 o'clock

Definition of coxologist and stability based on the analysis of changes in resistance and temperature gradient in the layer of catalyst during tests at low relationships steam/carbon and high contact loads consolename hydrocarbon feedstock (3,4 1/h, n-hexane and 0.6 1/h of benzene).

The temperature gradient on the layer of catalyst is determined at the test as the temperature difference in the upper and lower parts of the loading of the catalyst ( T=To-Tlogin).

The stability of the catalysts har is ).

In the selected experimental conditions the instability of the active component appears as a decontamination oxidative functions of the catalyst, leading to the deposition of coke on its surface and increase the pressure drop in the catalyst bed to be registered as a change in differential pressure during the test (PKon/ Pbeg). The destruction of the catalyst under the action of kokoulina leads to a rapid increase of pressure drop. For comparison catalysts with relatively high kokkotaskostas (accumulation of carbon is absent or minimal PKon/Pbeg1,00-1,05) further analyzed the carbon content in the unloaded samples.

The results of comparative tests of the catalysts are given in table. 2.

1. CATALYST FOR STEAM REFORMING of NAPHTHA AND REFINERY GASES, including an active portion containing oxides of Nickel, aluminum, magnesium, and media on the basis of aluminum oxide, characterized in that the active part further comprises oxides of calcium and potassium in the following content of components in the catalyst, wt.

Nickel oxide 3,0 8,0

Aluminum oxide 0,65 1,80

Magnesium oxide 0,45 1,65

Calcium oxide 0,35 1,40

The potassium oxide 0,75 3,35
4(Si4O10)(OH)8when the next content, wt.

Kaolin 2,0 8,0

Alumina Rest

 

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1 tbl, 3 ex

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