The method of purification of hydrogen from the oxygen-containing impurities and method of preparation of catalyst for implementation

 

(57) Abstract:

The invention relates to processes for the catalytic purification of hydrogen-containing gas from the oxygen-containing impurities, in particular carbon oxides, and to the technology of preparation of mixed catalysts and can be used in the chemical industry. The invention consists in carrying out the method of purification of hydrogen-containing gas from the oxygen-containing impurities, including hydrogenation to methane in the presence of a catalyst containing, by weight. %: Nickel oxide 25,0-52,0; chromium oxide 8,0-27,0; carbon of 0.4 to 6.0; manganese oxide (1U) 0,4-2,5; zirconium oxide 0,4-11,5; and the hydrogenation is carried out at 120-170oC. the Catalyst was prepared by mixing pre-processed and decontaminated Nickel catalyst with chromic acid for 0.4 3 h, then the introduction of a mixture of adjuvants in the ratio of the deactivated catalyst: chromium oxide: activated carbon: manganese oxide and/or zirconium oxide, is equal to 1:(0,2-0,6):(0,01-0,2):(0,01-0,12) respectively, and then the mixture was added a carbonate or bicarbonate of Nickel. 2 S. and 3 C.p. f-crystals, 2 tab.

The invention relates to processes for the catalytic purification of hydrogen-containing gas from the Cove and can be used in the chemical industry.

A known method of purification of hydrogen from the oxygen-containing impurities by hydrogenation to methane in the presence of a catalyst containing wt. NiO 25-40; Cr2O310-20; Al2O340-65 at a temperature of 160aboutC and flow rate of gas to 5000 h-1, (Ed. mon. USSR N 1152127, class B 017 J 37/04, 1985 prototype.

The main disadvantage of this method is the use of high-purity raw materials and scarce species of metal oxides NiO, Cr2O3, Al2O3. The disadvantage of operating catalysts are high-temperature process, a small flow rate of gas (not more than 5000 h-1).

Also known preparation method of catalyst for chemical processes by mixing in an aqueous medium at elevated temperature aluminum component with chromic anhydride in a weight ratio of: 1:(0,68-1,0), the introduction of the mixture of activated carbon, oxide or carbonate of manganese and/or oxide or hydroxide of zirconium, at mass ratio in terms of oxides: chromium oxide: aluminum oxide:activated carbon:manganese oxide and/or zirconium oxide 1:(0,4-2,5):(0,01-0,12):(0,01-0,12) within 1-3 h, with further mixing the obtained basis of the catalyst carb is the use of mixture into granules and their heat treatment at 80-280aboutC.

There is a method of cooking technology and allows to obtain an active catalyst that meets modern and promising technology for the production of ammonia, but in the process of making use of expensive high-purity fine chemicals qualifications "h", "analytical grade", "CHP", which for getting them require a large number of stages, from extraction of ores to purification from impurities, cost of labour, energy, material resources, manifested ultimately in the cost of raw materials. Yearly consumption of high-purity gastromony salts of the metals industry significantly reduces the inventory of expensive and scarce Nickel and other components, exacerbating the shortage of metals, energy and effort.

The method does not allow for the use of deactivated poisoned catalytic poisons (monoethanolamine, grey) and recrystallized in the operation of the catalyst. After deactivation of the catalyst, as a rule, goes to the dump, and in the best case dealt businesses in the recycling non-ferrous metals.

The aim of the invention is the creation of a technology for purifying the hydrogen-containing gas from the oxygen-containing impurities, Auber, and at the same time providing the possibility of obtaining a catalyst of the partially spent production waste, which reduces the cost of the process.

This is solved by the method of purification of hydrogen from the oxygen-containing impurities, including hydrogenation to methane in the presence of a catalyst, which use a catalyst containing components in the following ratio, wt. Nickel oxide 25,0-52,0; chromium oxide 8,0-27,0; carbon of 0.4 to 6.0; manganese oxide (IV) of 0.4-2.5 and/or zirconium oxide of 0.4-11,5; and the hydrogenation is carried out at 120-170aboutC.

The task is also solved by a method of producing a catalyst for purification of hydrogen from the oxygen-containing impurities, comprising mixing in an aqueous medium at elevated temperature aluminium-containing component with chromic anhydride, the additional introduction of a mixture of additives, activated carbon, oxides or carbonates of manganese and/or oxides of zirconium, mixed with carbonate of Nickel, followed by molding the mass into pellets and heat treatment, which as aluminum and Nickel-containing component use pre-processed decontaminated Nickel catalyst which is dissolved in a chromic acid in the nome of the deactivated catalyst:chromium oxide:activated carbon:manganese oxide and/or zirconium oxide is equal to 1:(0,2-0,6):(0,01-0,2):(0,01-0,12) accordingly, and the resulting mass is fed on a mixed carbonate or bicarbonate of Nickel. When a carbonate or bicarbonate of Nickel is introduced into the mass ratio in terms of oxides is equal to the deactivated catalyst:Nickel oxide 1:(0.2 to 0.4), respectively. Pre-processing of the decontaminated Nickel catalyst carried out with an organic acid at a mass ratio of acid catalyst is equal to 1:(0,02-0,1), respectively.

As the organic acid is used compounds from the group of oxalic, acetic, citric malic, formic.

The invention consists in the creation of technology for catalyst for purification of hydrogen from the oxygen-containing impurities, as raw materials, for which use of the deactivated catalyst containing oxides of Nickel, as activator compounds of hexavalent chromium, which allows the synthesis process of dispersing the active Nickel and aluminum components to structure the composition of obtaining bichromate metals and intensify the introduction of additives, coal, manganese and/or zirconium oxide, thereby to completely restore active properties and thermal stability of the catalyst after the processes PLA is 120-170aboutWith under soft conditions. This mode allows to reduce the possibility of thermal recrystallization of the active component of Nickel, to increase the service life of the catalyst, to increase the RMS speed of gas to 6000-7000 h-1.

The proposed method of preparation of the catalyst is as follows. Deactivated (Ni) process the catalyst disintegrate on vibro - or ink-jet or ultrasonic, or micro - or hydrodynamic, or bead mills, mixed with chromic anhydride and dissolved Nickel component. Activated Nickel catalyst disintegrate, mixed in the aqueous medium with chromic anhydride at a ratio of solid:liquid (T:W) of 1: (0,68-1,0), dissolved at a temperature of 30-70aboutWith over 0.4 to 3 hours active Nickel component and oxidizes in the presence of the catalyst of the catalytic poison of monoethanolamine-chromic acid, optionally injected into the mixture of activated carbon, oxide or carbonate of manganese and/or the oxide or hydroxide of zirconium in a ratio in terms of oxides:deactivated catalyst: chromium oxide: ACTIVIA & coal:manganese oxide and/or zirconium oxide 1: (0,2-0,6): (0,01-0,12): (0,01-0,12), the mixture is brought to a ratio of T:W 1: (0,2-0,4)that is niteline at the stage of mixing with catalytic additives are introduced, or basic Nickel carbonate at a ratio in terms of oxides:deactivated catalyst:Nickel oxide 1:(0,2-0,4), intended for supplying catalyst composition of mahanirvana meet THE 103-03-398-87.

Additional treatment of the deactivated catalyst with an organic acid, for example oxalic when the ratio of the deactivated catalyst: organic acid of 1:0,1-0,02, intended to displace the catalytic poisons, provides developed surface of the catalyst, to increase the porosity and accessibility.

The disintegration of the decontaminated Nickel-containing catalyst is produced to increase the surface of the catalyst mass, and access of chromic acid to the active Nickel component, which, interacting in predetermined ratios T:W, temperature range and time translates not active, formed during operation micellaneous spinel, soluble in connection bichromate Nickel, aluminum component in the reaction develops surface with 10-20 m2/g to 150-300 m2/,

As the organic acid is used compounds from the group of oxalic, acetic, citric, malic, formic. This allows you to displace a catalytic poison sulfur from the deactivated catalyst account more elektromreza the I the invention is illustrated by the following examples.

P R I m e R 1. The deactivated catalyst HKM-1 grind, load in a mixing apparatus, hydrate with water at a ratio of T:W 1:1, add pre-otwieranie amount of chromic anhydride according to the ratio of the deactivated catalyst: chromic anhydride:activated carbon: manganese carbonate in terms of oxides is 1:0,2:0,01 0,01 to, stirred for three hours, oxidizing catalytic poison monoethanolamine. Oxidation record spontaneous temperature increase from 20 to 50-70aboutWith and dissolve the Nickel component, add according to the ratio of the weighed quantity of activated carbon and manganese carbonate, adjusted to a moisture content of 1:0,35, form the mixture into pellets, granules thermoablative at a temperature of 280aboutC.

Testing a sample of the catalyst in example 1 and subsequent examples is carried out in an industrial apparatus when the composition of the gas containing carbon monoxide is from about 0.3 to about 1,040. of carbon dioxide from 0.0 to 0.3. to a residual content of 1 to 10-3about. at a pressure of from 1.5 to 2.5 MPa with high volume speeds up to 6000 h-1activity is judged at the lowest temperature that ensures the content of carbon oxides less than 1 of 10-3-3after preliminary overheating at 550 10aboutC for 10 h under a pressure of 3.0 MPa, flow rate 4000 h-1the content in the feed gas 0,3-0,7 about. And of 0.00-0.03 to about. CO2160aboutC.

Samples of catalysts for the process of mahanirvana, prepared as in example 1, but corresponding in composition within the defined relationship, physical characteristics, activity indicators are given in table. 1.

In the sample according to example 2 in the deactivated catalyst optionally being mixed with the activating additives injected according to the ratio in terms of oxides:deactivated catalyst:basic Nickel carbonate 1: 0,4.

In the sample 3 as the deactivated catalyst is used GIAP-16, according to the given ratio of injected Nickel component, and oxalic acid impose more directly at the stage of disintegration.

In the sample 4 as the deactivated catalyst is used GIAP-3-6N and shows perhaps the deactivated catalyst is used GIAP-17.

In the sample 6 as the deactivated catalyst is used HKM-4A.

Sample 7 is prepared as sample 1, but additionally after mixing the mass with catalytic additives injected according to the ratio of oxalic acid.

In the sample according to example 8 shows the capability of the catalyst prepared from the deactivated contact-2 at a minimum temperature of 120aboutC.

Sample 9 is prepared by a known method.

As the sample 10 have the standard sample of catalyst HKM-4A (TU 113-03-398-87).

In example 11 are shown out of proportion and blend mode of the mass, it is shown that reducing the time of mixing the mass, mixing temperature (15aboutC) does not allow to obtain the catalyst that meets the requirements of the activity for catalysts mahanirvana.

On the basis of the conducted research and development activities to define the optimal ratio of components and parameters of the method of preparation.

The results of the experimental work within the specified limits and ratios allow to obtain catalysts, activity exceeding not only the known catalysts mahanirvana, such as HKM-1, the NYC-4A, HKM-nomia 7 Gcal per 1 ton of product (NH3), i.e., catalysts that meet the requirements of the activity according to the method prototype.

Additional introduction the preparation of the catalyst of the Nickel component allows you to use not only the deactivated catalyst in mahanirvana, but the catalysts for methane conversion, such as GIAP-3-6N, GIAP-16, GIAP-17, GIAP-18, 19.

Additional processing of the catalyst is an organic acid can partially clean the catalyst from sulfur compounds and to increase the activity of the samples, with the catalyst mahanirvana introduction organic acids it is better to make at the last stage of cooking after the introduction of catalytic additives for the deactivated catalysts for methane conversion in the first stage of disintegration of the deactivated catalyst, which provides the reaction of the deactivated catalyst is an organic acid in the solid phase.

Use instead of oxalic other types of acids (acetic, formic, malic, citric) provides similar results reflected in the table. 1.

P R I m m e R 2 (method of purification of hydrogen-containing gas) cat. min Ni min toHYDR.

P R I m e R 3 (method of purification in a/c gas, kaSS="ptx2">

When using the invention can be obtained the following advantages: to obtain a catalyst having high activity and stability, which when applied provides increased flow rate of gas to 6000 h-1or lowering of the load device by 10-15% and correspondingly reducing expenditure ratios of catalyst per unit of output.

1. The method of purification of hydrogen from the oxygen-containing impurities, including hydrogenation to methane in the presence of a catalyst, characterized in that the use of catalyst containing components in the following ratio, wt. %:

Nickel oxide - 25,0 - 52,0

The chromium oxide - 8,0 - 27,0

The carbon of 0.4 to 6.0

Oxide manganese (IV) - 0,4 - 2,5

Zirconium oxide is 0.4 - 11,5

and the hydrogenation is carried out at 120 - 170oC.

2. A method of producing a catalyst for purification of hydrogen from the oxygen-containing impurities, comprising mixing in an aqueous medium at elevated temperature aluminium-containing component with chromic anhydride, the additional introduction of a mixture of additives, activated carbon, oxide or carbonate of manganese and/or oxides of zirconium, followed by mixing with Nickel carbonate, forming masses in grandebretagne processed decontaminated Nickel catalyst, which is dissolved in chromic acid for 0.4 to 3.0 h, and then carry out the introduction of the mixture of components at a mass ratio in terms of oxide catalyst : chromium oxide : activated carbon : manganese oxide and/or zirconium oxide, is equal to 1 : (0,2 - 0,6) : (0,01 - 0,2) : (0,01 - 0,12) respectively, and the resulting mass is fed to the mixing with the carbonate or bicarbonate of Nickel.

3. The method according to p. 2, wherein the carbonate or bicarbonate of Nickel introduced in the mass ratio in terms of oxides is equal to the catalyst : Nickel oxide 1 : (0.2 to 0.4), respectively.

4. The method according to PP.2 and 4, characterized in that the pre-processing of the decontaminated Nickel catalyst carried out with an organic acid at a mass ratio of acid catalyst is equal to 1 : (0,02 - 0,1), respectively.

5. The method according to PP. 2 to 4, characterized in that the organic acid is used oxalic acid.

 

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FIELD: hydrogenation-dehydrogenation catalysts.

SUBSTANCE: invention relates to catalysts used in isoamylenes-into-isoprene dehydrogenation process and contains, wt %: iron oxide 62-75.4, potassium carbonate 12-21.5, chromium oxide 1-3, potassium hydroxide 0.5-2.5, sulfur 0.1-2.0, ammonium nitrate 0.1-2.0, silicon dioxide 1-5, calcium carbonate 1-5, and cerium nitrate 1-3.

EFFECT: increased mechanical strength, resistance to saturated steam and moisture, and stability during long-time operation.

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