The catalyst for steam reforming of hydrocarbons

 

(57) Abstract:

The essence of the invention: catalyst for steam reforming of hydrocarbons contains the Mac. Nickel oxide 5,9 12,5; aluminum oxide 1,25 2,45; magnesium oxide 0,15

0,66; oxide of lanthanum 0,49 1,96; cobalt oxide of 0.20 to 1.02; or an oxide of neodymium 0,46 or oxides of cobalt and neodymium 0,27 0,55. 1 C. p. F.-ly, 2 tab.

The invention relates to the production of catalysts for steam reforming of hydrocarbons, including naphtha and will be able to find its application for hydrogen, nitric 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 0 Mg; 0.08 To 0,71 Na2O; 0,32-2,85 SiO2; -Al2O3rest [1]

The main disadvantage of this catalyst is the 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 Al2O3; 0,5-impregnation of the carrier of the composition based on alumina, 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. Betting 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, 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/s=3.5 to 3.8 and bulk velocity in the liquid raw material 0,8-1,1 1/h

Steam reforming of hydrocarbons most effectively runs on Nickel catalysts supported type, promoted by oxides of transition elements that regulate their activity and selectivity. Known application for promotion these catalysts lanthanum oxide [2]

Lack of catalysts supported type is their instability, which is manifested in the gradual pottow is stepped destructive oxidation of the carbon skeleton of the molecule lattice oxygen of the oxide of Nickel. The instability of the active part of the catalyst caused by the suppression of recycline surface water vapor, reducing the rate of oxidation of the carbon skeleton of the molecule, blocking oxidative centers the seal products, i.e., the oxidation activity of the catalyst leading to coking and destruction of the catalyst.

Improving the efficiency of oxidative functions of the catalyst can be achieved by selection of appropriate promoters. Recycline surface of the proposed catalyst is due to the dissociative adsorption of water vapor, mainly with the formation of hydroxides of rare earth elements. Promotion of the active component of the catalyst is carried out leads to a decrease of thermal stability of hydroxides REE (TFSLa(OH)3>700aboutC. TFSNd(OH)3=300-350aboutC) and accelerated recycline active component.

The rate of oxidation of adsorbed hydrocarbons lattice oxygen of the oxide of Nickel is associated with thermal stability of the anionic lattice of Nickel oxide, which can be enhanced by the promotion of cobalt (TFSNi2O3= 600aboutS, TFSCO2ABOUT3=895aboutWith the lyst allows to obtain a catalyst with high kokkotaskostas and stability, suitable for steam reforming Kokshenov raw materials with large contact loads.

The invention consists in the establishment of the catalyst caused the type having a composition of the active component in addition, the promoters of the oxides of cobalt (111) and/or neodymium, significantly increases coxologist and oxidative stability functions of the catalyst. As a carrier, the catalyst contains-Al2O3or-Al2O3containing, by weight. 1,5 Cao and MgO of 0.5 applied to optimize the size of the crystallites AND2ABOUT3. Or the catalyst contains as a carrier Al2O3.

The proposed catalyst contains oxides of the metals in the following ratio, wt.

Nickel oxide 5,9-12,5

Aluminum oxide 1,25-2,45

Magnesium oxide 0,15-0,66

The oxide of lanthanum 0,49-1,96

The cobalt oxide 0,20-1,02

or neodymium Oxide 0,46

or Oxides of neodymium and

cobalt 0,27-0,55

In contrast to the catalyst of the prototype of the proposed catalyst allows steam reforming raw material containing 15 wt. aromatic hydrocarbons, at loads up to 4l/h on raw, with reduced content of N2O/s without kokoulina.

After each impregnation the catalyst is dried and calcined to decompose the nitrate salts. The final calcination of the catalyst is performed at a temperature below 500aboutWith aged not less than 2 hours Get a catalyst of the following composition, wt.

Nickel oxide 10,0

Aluminum oxide 1,90

Magnesium oxide 0,43

The oxide of lanthanum 1,00

The cobalt oxide 0,26

The neodymium oxide 0,12

The media and the Rest

P R I m m e R 2. To prepare 1000 g of catalyst on 875,5 g media (-Al2O3) with a porosity of 0.32 cm3/g for three impregnation aqueous solution is applied 358,2 g of Nickel nitrate setevogo Ni(NO3)26H2O (92.0 g NikO); to 128.8 g of aluminum nitrate deviations ASUB>O (4.0 g MgO); 23,92 g of lanthanum nitrate setevogo La(NO3)36H2O (9.0 g La2O3); 7,02 g of cobalt nitrate setevogo With(NO3)26H2O (2.0 g Co2ABOUT3).

After each impregnation the catalyst is dried and calcined to decompose the nitrate salts. The final calcination of the catalyst is at a temperature below 500aboutWith aged not less than 2 hours Get a catalyst of the following composition, wt.

Nickel oxide 9,2

Aluminum oxide 1,75

Magnesium oxide 0,40

The oxide of lanthanum 0,90

The cobalt oxide 0,20

The media and the Rest

P R I m e R 3. To prepare 1000 g of catalyst on 864,3 g media ( -Al2O3) with a porosity of 0.32 cm3/g for three impregnation aqueous solution is applied 358,2 g of Nickel nitrate setevogo Ni(NO3)26H2O (92.0 g NiO); 139,8 g of aluminum nitrate deviational Al(NO3)3x x9H2O (19,0 g Al2O3); 28,63 g of magnesium nitrate setevogo Mg(NO3)26H2O (4.5 g MgO); 26,58 g of lanthanum nitrate setevogo La(NO3)36H2O (10.0 g La2O3); 35,80 g of cobalt nitrate setevogo With(NO3)26N2About (10.2 g Cox salts. The final calcination of the catalyst is at a temperature below 500aboutWith aged not less than 2 hours

Get a catalyst of the following composition, wt.

Nickel oxide 9,2

Aluminum oxide 1,90

Magnesium oxide 0,45

The oxide of lanthanum 1,00

The cobalt oxide 1,02

The media and the Rest

P R I m e R 4. To prepare 1000 g of catalyst on 919,4 g media ( -Al2O3) with a porosity of 0.25 cm3/g for three impregnation aqueous solution is applied 229,7 g of Nickel nitrate setevogo Ni(NO3)26H2O (59.0 g NiO); 92,0 g of aluminum nitrate deviational Al(NO3)39H2O (12.5 g Al2O3); of 9.55 g of magnesium nitrate setevogo Mg(NO3)26H2O (1.5 g MgO); 13,02 g of lanthanum nitrate setevogo La(NO3)36H2O (4.9 g La2O3); is 4.21 g of cobalt nitrate setevogo With(NO3)26H2O (1.2 g Co2ABOUT3); 3,91 g of neodymium nitrate setevogo Nd(NO3)36H2O (1.5 g Nd2ABOUT3).

After each impregnation the catalyst is dried and calcined to decompose the nitrate salts. The final calcination of the catalyst is at a temperature below 500>Aluminum oxide 1,25

Magnesium oxide 0,15

The oxide of lanthanum 0,49

The cobalt oxide 0,12

The neodymium oxide 0,15

The media and the Rest

P R I m e R 5. To prepare 1000 g of catalyst on 819,7 g media ( -Al2O3with a content of 1.5 wt. CaO and 0.5. MgO, GIAP-8 GOST) with a porosity of 0.35 cm3/g for three impregnation aqueous solution is applied 486,6 g of Nickel nitrate setevogo Ni(NO3)26N2O (125,0 the NiO); 180,3 g of aluminum nitrate deviational Al(NO3)39H2O (24.5 g Al2O3); 41,99 g of magnesium nitrate setevogo Mg(NO3)26H2O (6.6 g MgO); 52,10 g of lanthanum nitrate setevogo La(NO3)36H2O (19,6 g La2O3); 11,99 g of neodymium nitrate setevogo Nd(NO3)36H2O (4.6 g Nd2O3).

After each impregnation the catalyst is dried and calcined to decompose the nitrate salts. The final calcination of the catalyst is at a temperature below 500aboutWith aged not less than 2 hours

Get a catalyst of the following composition, wt.

Nickel oxide 12,5

Aluminum oxide 2,45

Magnesium oxide 0,66

The oxide of lanthanum 1,96

The neodymium oxide 0,46

The media the Rest of the Mac. CaO and 0.5. MgO) with a porosity of 0.35 cm3/g for three impregnation aqueous solution is applied 365,0 g of Nickel nitrate setevogo N1(NO3)2H2O (94,0 g NiO); 117,7 g of aluminum nitrate deviational Al(NO3)39H2O (16.0 g Al2O3); 38,17 magnesium nitrate setevogo Mg(NO3)26H2O (6.0 g MgO); 39,87 g of lanthanum nitrate setevogo La(NO3)36H2O (15.0 g La2O3); to 12.28 g of cobalt nitrate setevogo With(NO3)26H2O (3.5 g Co2ABOUT3), a total of 5.21 g of neodymium nitrate setevogo Nd(NO3)26H2O (2.0 g Nd2O3).

After each impregnation the catalyst is dried and calcined to decompose the nitrate salts. The final calcination of the catalyst is at a temperature below 500aboutWith aged not less than 2 hours

Get a catalyst of the following composition, wt.

Nickel oxide 9,4

Aluminum oxide 1,60

Magnesium oxide 0,60

The oxide of lanthanum 1,50

The cobalt oxide 0,35

The neodymium oxide 0,20

The media and the Rest

The composition of the catalysts according to examples 1-6 are shown in table. 1.

P R I m e R 7. For testing coxologist and stability offered the Xan with benzene containing 15 wt. benzene in maxogenol close to nafta. The conversion is carried out at 500aboutWith a molar ratio of N2O/s=2.0 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 conversion 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).

In the upper layer of the catalyst (in the direction of reagents) when steam reforming is dominated by the endothermic reaction of the oxidative degradation of the carbon skeleton of the molecules of hydrocarbons, and in the lower exothermic hydrogenation reactions and additional oxidation of the primary products of oxidative degradation.

Therefore, when the degree of conversion of the hydrocarbons in the C1products (CH4, CO, CO2is equal or close to 100% so is it part of the loading of the catalyst (T=Tn-Tin), is proportional to the activity in the process of destructive oxidation of hydrocarbons and can be used as an integral characteristic of oxidative activity.

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 stability of the catalysts are characterized by a relative change of the temperature gradient during the test ( TKon/ Tbeg).

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

1. The CATALYST for STEAM reforming of HYDROCARBONS, including an active portion containing oxides nick the congestion further comprises an oxide of cobalt (III) and/or neodymium oxide with the following content of components in the catalyst, wt.

Nickel oxide 5,9-12,5

Aluminum oxide 1,25-2,45

Magnesium oxide 0,15-0,66

The oxide of lanthanum 0,49-1,96

The cobalt oxide 0,20-1,02

or

The neodymium oxide 0,46

or

The oxide of cobalt and neodymium 0,27-0,55

The media and the Rest

2. The catalyst p. 1, characterized in that as the carrier used a-alumina, containing 1.5 wt. CaO and 0.5. MgO.

 

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