SU730362A1 - Catalyst for vapour conversion of hydrocarbon gases - Google Patents

Description

I

{The invention relates to a process for the production of catalyst catalysts for the process of steam reforming of hydrocarbon gases.

Promoted alloyed 1-catalyst catalysts based on aluminum and nickel with an oxide surface are known, for example, nickel-chromium Cl Cl-2 aluminogellose.

Closest to the proposed technical essence and the achieved effect is a catalyst for steam; conversion of hydrocarbon gases on the basis of a leached nickel-aluminum alloy with a promoter supplement Ibj I3j.

A disadvantage of the known catalysts is their high bulk density, which is economically disadvantageous, since as the weight increases, the weight of the catalyst increases to obtain a unit volume of hydrogen.

In tab. 1 shows the data on the weight of the known catalysts.

Table 1

Bulk weight, g / cm

Analyzer

Apyumonkelkhromovy2, 1-2,3

(Alyumonkelzhelzvyvyy2, 0-2,2

 Alumon ikel niobium-2.0-2.2

ten

In addition, the catalyst activity, with increasing process temperature to

15 EOO C and more decreases due to the sintering of the active component due to the low thermal stability.

For example, the activity of a known aluminum nickeliobium catalyst decreases after 2-4 hours of the steam reforming process at, and then the catalyst works satisfactorily at 79 ° -820 ° C, gas flow rate of 3 ° 80 ° -1000 h and the ratio of steam to gas of 2-3: 1 the catalyst is even less thermostable. Its activity begins to drop as the process temperature increases to 5 ° C in 2 hours, and at 870 ° C in 5 minutes. After complete recrystallization of the active component, the catalyst activity does not change, and to obtain a dry converted gas with residual methane content {2 vol%, it is necessary to increase the process temperature to 880-920 C. The dependence of the activity of a known catalyst on the temperature is presented in Table. 2. Table 2

This catalyst can be used for the production of process gases (reducing or gas synthesis) with low CO content when carrying out the process at 92 O-960 C.

The purpose of the invention is to reduce the bulk density of the catalyst and increase its service life.

The delivered chain is achieved in that the steam reforming catalyst is used. of hydrocarbon gases in the base of the leached alloyed aluminum alloy additionally contains promotnuyuyu additive - Kalysh, barium or magnesium at the next content of the components | weight.%:

Calcium barium or magnesium O, 5-5, O

Nnkap45, O-48, O

Aluminum Else

The catalyst is prepared as follows.

In a graphite crucible load 2OO g of aluminum and placed in a furnace electric furnace heated to 100О-1100 С.

196 g of nickel shavings are added to the crushed aluminum, and then 4 g of metallic barium is added under stirring. After thorough mixing, the melt is poured into a Stans pan, which is immediately immersed in cold water, and the alloy code is 380 g (95%). The composition of the alloy in VSS,% of the charge as follows:

Aluminum 5O

Nickel49

Barium .1

The pellets were crushed to the desired granule size, placed in a porcelain cup and filled with 2OO ml of water, then 200 MP of 40% alkaline solution was gradually added, notwithstanding the temperature of the leaching process to be within 92-96 ° C. Leaching process It lasts for 3-4 hours. After this, the catalyst is washed with water until the neutral reaction of the washed water and, draining the water in a wet state, placed on an electric plate at 1502OO C, tightly closing the headlight cover 5 7303626

head glass At the same time, the surface x and, when used, does not require a precatalyst, which is gradually oxidized by fatigue reduction. Anaphogenic acid is produced by the action of water vapor and oxygen catalysts are prepared that contain air for 2-2.5 hours and in varying amounts of Ca, Ba and Md, while the vessel is cooled. The resulting 5 The compositions of the catalysts obtained, the catalyst is stored at the access of air, are given in Table 3. Test kataetizatorov illustrated by the following examples. The examples of a steel tubular 1seactor are charged with 20 mp of a fused-aluminum alyumolecol catalyst, containing 2% of a calf in charge with a bulk weight of 1.72 g / cm and a natural flow; gas with a space velocity of 2,000 hours at a steam-to-gas ratio of 2.9: 1 and temperatures of 700 C. At the same time, the composition of the dry converted gas is as follows,% by volume, CO 11.74, CO 10.45 and CH O, 81. PRI mme R 2. In contrast to Example 1, a nickel-alumina catalyst (bulk density 1.76 g / cm) containing 2.0 wt.% Barium was charged to the reactor. and determine its activity at 7OOC. The volumetric rate of natural gas is 31OOH and the ratio of steam to gas is 3: 1. The residual methane content is only 0.47% by volume.

Table 3 The composition of the dry converted gas is as follows,% by volume: H277.84, CO 11.00, Qpa 1O, 69. Example 3. In contrast to Examples I and 2, the activity of the alumi-nickel-barium (barium 2, Ove% per charge) catalyst is determined after 30 hours of the process of steam reforming of natural gas at 900-92 ° C. The catalyst is in a stable state without a decrease in activity converts natural gas at 800 ° C, a gas volumetric rate of more than 10–10 and a steam to gas ratio of 1.4: 1. The composition of the dry converted gas is as follows, vol.%: H276.53, CO 18.80, CO 5.04 and CH. 0.63. Example 4. In contrast to p | 5merov 1,2 and 3, is loaded into the reactor alumina-nickel catalyst containing 1.5 weight. % magnesium on charge with a net weight of 1.90 g / cm and pass natural, 7 ..,. gas at a volume ratio of 2.0: 1 and a temperature of 750 C. At the same time, the composition of the dry converted gas is as follows,% by volume: Hg 75.42, CO 17.85, CO 5.47, 2 6 Example 5. In contrast to examples 1-4, the activity of an alumino-nickel-type catalyst containing ZR% by weight in a mixture of calcium with a bulk weight of 1.66 g / cm is determined after 10 hours of steam reforming of natural gas at 90 ° -190 ° C After that, the catalyst converts natural gas at 7OO C, a gas flow rate of 1000 h and a steam-to-gas ratio of 3.0: 1, while the composition of the dry gas is RH gas: the following volume: M. ЖЙ1, CO 9.04, COg 11.67, СН The proposed catalyst has a relatively high bulk density up to 1.661585 is more thermostable than the known one. When the process is carried out at high temperatures (90O and more), their activity begins to decrease due to sintering of the active component only after 10-30 hours of work, and then to obtain dry converted gas with a minimum content of a meter, the process is carried out at 750-800 ° C , gas flow rate 1OOO-15OO h The dependence of the activity of the proposed catalyst on temperature is presented in Table 4. Table4

Claims (1)

Claim A catalyst for steam conversion of hydrocarbon gases based on leached nickel-aluminum alloy with a promoting additive, characterized in that, in order to reduce the bulk density of the catalyst, increase TsNIIPI Order 1407/1 The proposed catalyst has a relatively low bulk density of up to 1,661.85 g / cm ³ and is more thermostable compared to the known one. When the process is carried out at high temperatures (900 ° or more), their activity begins to decrease due to sintering of the active component only after 10-30 hours of work, and then to produce a dry converted gas with a minimum methane content, the process is carried out at 750-800 ° С gas volumetric velocity of 1000-1500 h The dependence of the activity of the proposed catalyst on temperature is presented in table. 4. thermostability and increase its service life, the starting alloy contains as an additive-calcium, barium or magnesium in the following components, wt.%: Calcium, Barium or Magnesium 0.5-5.0 Nickel 45.0-49.0 Aluminum Else