Catalyst for removing carbon monoxide from air

FIELD: gas treatment.

SUBSTANCE: catalyst contains alumina-supported palladium oxide, 0.80-2.54%, copper salt, 3.09-11.79%, promoter represented by phthalocyanine complex with iron or cobalt, 0.10-1.00%, and 0.50-3.00% of polyatomic alcohol.

EFFECT: enhanced efficiency of removing carbon monoxide as well as accompanying sulfur-containing impurities.

1 tbl, 21 ex

 

The present invention relates to the field of air purification, in particular for catalyst for purification of air from the carbon monoxide, and can be used, for example, in personal (masks, respirators, gas masks) and collective protection (attachments for air-conditioners, air purification in residential, public and industrial premises).

Known catalyst for air purification from carbon monoxide [US, 4521530, 4.06.1985]. This catalyst contains deposited on a porous carrier (aluminum oxide) salt of palladium, two copper salt, Nickel salt.

The catalyst was prepared by impregnation of the support with an aqueous solution of salts at a temperature of about 25°followed by filtration, air drying and activation at 200°C. the Catalyst allows to reach the degree of air purification from carbon monoxide up to 99% at the time of contact from 0.13 to 0.4 C. However, the catalyst is sufficiently active only in a narrow range of concentrations of carbon monoxide in the air (at 125 mg/m3=107 ppm and below). In addition, there are no data on the stability of the catalyst to sulfur-containing gases (H2S, SO2available in air, and the change in humidity.

Closest to the claimed technical essence and the achieved result is the catalyst for purification of air from monoxide in the of Lerida, containing deposited on a porous carrier salt, palladium salt of copper and a promoter [EP, 0238700, 23.01.91]. As a promoter, the catalyst contains a compound or vanadium compound of vanadium in combination with a compound of phosphorus. This is a known catalyst was prepared in two ways.

The first involves the impregnation of the support in an aqueous solution containing a palladium salt, a salt of copper and a promoter, followed by heating the resulting product and evaporation of the water.

According to the second method previously applied to the carrier promoter with subsequent heat treatment of the resulting product at a temperature not lower than 100°C. Then applying promoted on the media palladium salt and a copper salt with the aforementioned method get the catalytic Converter.

However, this known catalyst does not allow you to bring the content of carbon monoxide in the purified air to a concentration below the maximum permissible level (MPL) for the working zone (20 mg/m3) at a contact time of 0.3 sec.

The basis of the offer of the invention is the development of a catalyst that effectively clears the air of carbon monoxide. The content of the latter in purified air should not be higher than 20 mg/m3while air purification from sulfur-containing compounds.

The problem is solved by the fact that the catalyst for purification of air about the carbon monoxide, containing deposited on aluminum oxide, palladium salt, a salt of copper and a promoter according to the present invention contains as a promoter phtalocyanines complex of iron or cobalt and polynuclear alcohol in the following ratio, wt.%:

Salt of palladium0,80-2,54
Salt of copper3,09-to 11.79
Phtalocyanines complex of iron or cobalt0,10-1,00
Polynuclear alcohol0,50-3,00
Aluminium oxiderest

The main advantage of the proposed catalyst, compared with the prototype and analogues, is the ability to achieve relatively safe content of carbon monoxide in the air (MPC working area of 20 mg/m3in the case of change in a wide range of the original content of carbon monoxide in the purified air (100-10000 mg/m3), humidity and gas flow rate of the gas mixture (DHW) to 12000 h-1(contact time of 0.3 s) and content DHW sulfur-containing compounds to 35 mg/m3, hydrocarbons up to 0.1% (1000 ppm).

The versatility and stability of the proposed catalyst allows to use it both for air cleaning of residential, public and industrial premises is ri relatively low concentrations of carbon monoxide (2-20 MAC), and in cases when the concentration of carbon monoxide in the air reaches 1% and above (vysokokachestvennye jobs, street intersections in the formation of traffic jams, underground Parking, rooms for testing internal combustion engines, fires etc).

The use of catalyst PdCl2-CuCl2aluminum oxide", prepared by the same method, it is not possible to reduce the content of carbon monoxide in the mixture to the MPC (20 mg/m3) (see example 1).

As a salt of palladium offer the catalyst may contain any salt of palladium, for example, chloride or bromide, palladium (II). When this lower limit salt of palladium due to the fact that the catalyst containing fewer PdCl2that does not clear DHW containing ˜ 100 mg/m3carbon monoxide, up to concentrations below 20 mg/m3. The content of palladium chloride(II) above 2,54% wt. increases the cost of the catalyst without substantial increase in catalytic activity. As a salt of copper, you can also use a variety of copper salts (chloride, bromide, sulfate). The salt content of copper is from 3.09 up to 11.79%. The higher the salt content of copper leads to a decrease in catalyst activity. When the content is less 3,09% wt. salts of copper (II) decreases the period of stable operation of the catalyst.

The top is the limit of the amount phthalocyaninato complex iron or cobalt (PCM) due to the limited solubility of the latter in water, consequently, limited the possibility of applying RSM to the media. Content phthalocyaninato complex iron or cobalt less than 0.10% does not increase the proposed activity of the catalyst compared to a catalyst containing only salts of palladium and copper.

Deposition on the catalyst of a large number of polynuclear alcohol (above 3,00%) leads to decreased activity. The content of polynuclear volume of less than 0.50% is not enough for stable operation of the catalyst.

The catalyst was prepared by the method of "cold soaking" in the following way. Weighed the right amount of aluminum oxide (fraction 1-2 mm, or 0.5-1 mm). Counted the required number of salts of palladium, copper, phthalocyaninato complex iron or cobalt (RSM) and polynuclear alcohol. Sample salts of palladium, copper and RSM was dissolved in 10 ml of water by heating to 70°and With stirring until complete dissolution (˜15 min). After cooling the solution to room temperature, was added a portion of polynuclear alcohol and stirred for 2 minutes to dissolve the latter. In the flask with the solution was loaded media and kept for days at room temperature. Then the solution was filtered on a glass filter. The mother solution was tested for absence of damage to components known methods. The catalyst was dried on the filter in the current who's who of the ear, and then when heated. Thus obtained catalyst was used for air purification from carbon monoxide.

Testing of catalytic activity was performed in a glass reactor, which is a tube with a diameter of 20 mm with shelf for catalyst. The volume of the sample of the catalyst loaded in the reactor 5 ml. air Flow created by the compressor. Carbon monoxide is fed into the mixer gas from the Gasometer through a calibrated rheometer. The carbon monoxide concentration in the gas mixture (DHW) was monitored by gas chromatography (in the concentration range of 0.05 to 1.5% by vol.) either using Eclipse PCG-4-WITH-MK-with electrochemical sensor (in the range 0-0,05%. (500 ppm)). The humidity of the gas mixture was determined using a moisture meter IVTM-7. The concentration of hydrogen sulfide was measured using an electrochemical detector IPF-19.2.

Below are examples illustrating the implementation of the proposed technical solutions, not limiting its scope.

Example 1.

Weighed 5 ml aluminum oxide (fraction 1-2 mm). Mass media was 2.3 g Sample of palladium chloride (PdCl2) and copper chloride (CuCl2·2H2O) was calculated based on the required content of these components in the catalyst: PdCl2- 0,058 g (0.32 mmol, 2,40% by weight of the catalyst), CuCl2 ·2H2On - 0,217 g (1,27 mmol, 7,10% CuCl2from the mass of catalyst). Sample salts of palladium and copper was dissolved in 10 ml of water in a conical flask with a capacity of 50 ml under stirring while heating to 70° (˜15 min). After cooling the solution to room temperature in the flask with the solution was loaded aluminium oxide and maintained in one day at room temperature. Then the catalyst was filtered on a glass filter. The mother solution was tested for absence of damage to components known methods. The catalyst was dried on the filter in a stream of air for 15 min, and then at a temperature of 100±5°C for 1 h 45 minutes

Tests of the obtained catalyst was performed in a flow reactor (see above) at a temperature of 21°and flow rate 10000 h-1. The content of carbon monoxide in the feed gas was ˜1% vol. The humidity of the gas mixture (DHW) - 50% Rel. The content of carbon monoxide in the gas after cleaning 110 mg/m3the degree of purification 98,9%.

Examples 2-16 (table 1).

Weighed 5 ml aluminum oxide (fraction 1-2 mm). The required sample salts of palladium and copper, phthalocyaninato complex of the transition metal was dissolved in 10 ml of water in a conical flask with a capacity of 50 ml under stirring and heated to 70° (˜15 min). After cooling the solution to room temperature in the flask was added the avesco polynuclear alcohol, was stirred for 2 minutes, and then poured the aluminum oxide. In a further procedure for preparation of the catalyst coincides with the method described in example 1. The catalysts are shown in table 1, were tested at room temperature and flow rate DHW 12000 h-1(contact time of 0.3 sec). Duration of test 3 hrs. The results are given in table 1. In all cases, the content of carbon monoxide in the purified gas did not exceed 20 mg/m3(MPC working area).

Example 17.

The catalyst was prepared according to the method of examples 2-16 with the following content components: PdCl2- 2,43% wt., CuCl2- 3,09% wt., PcFe to 0.60 wt.%, diethylene glycol - 3,00% wt., Al2About3- the rest. The catalyst was tested at a temperature of 23°relative humidity DHW - 40% Rel., the content of carbon monoxide - 300 mg/m3, flow rate 12000 h-1(contact time of 0.3 sec). The tests were carried out for 55 hours. The catalyst is stable. The carbon monoxide concentration after purification 4±2 mg/m3.

Example 18.

The catalyst was prepared according to the procedure described for examples 2-16 with the following content components: PdCl2- 2,37% wt., CuCl2- 8,80% wt., PcFe - 0,100% wt., glycerin - 3,00% wt., Al2About3- the rest. The catalyst was tested at a temperature of 18°relative humidity DHW - 55% and the obsession of carbon monoxide in the original WAN 100 mg/m3. The tests were carried out for 200 hours. The catalyst is stable. The content of carbon monoxide in DHW after cleaning is 16±2 mg/m3.

Example 19.

The catalyst was prepared according to the procedure described for examples 2-16 with the following content components: PdCl2- 1,11% wt., CuCl2- 8,87% wt., PcFe to 1.00 wt.%, glycerin - 3,00% wt., Al2About3- the rest. The catalyst was tested at a temperature of 25°relative humidity DHW - 50%, the content of carbon monoxide to 1.00%, the content of a mixture of hydrocarbons (propane:butane = 3:1) to 1000 ppm. The loading of catalyst on DHW - 10000 h-1. The test duration is three hours. The catalyst is stable. The content of carbon monoxide in the purified air was 13±1 mg/m3.

Example 20.

The catalyst was prepared according to the procedure described for examples 2-16 with the following content components: PdCl2- 1,11% wt., CuCl2- 8,87% wt., PcFe - 0,50% wt., glycerin to 1.00 wt.%, Al2O3- the rest. The catalyst was tested at a temperature of 22°relative humidity DHW - 60% load for DHW - 10000 h-1. The source gas mixture contained 100 mg/m3carbon monoxide, 30 mg/m3sulfur dioxide, the rest is air. The test duration is two hours. During testing the activity of the catalyst snis who stayed at 5% relative.

Example 21.

The catalyst was prepared according to the procedure described for examples 2-16 with the following content components: PdCl2- 2,36% wt., CuCl3- 8,80% wt., PcFe - 0,50% wt., glycerin to 1.00 wt.%, Al2O3- the rest. The catalyst was tested at a temperature of 19°relative humidity DHW - 60% load for DHW - 10000 h-1. The source gas contained 100 mg/m3carbon monoxide, 25 mg/m3of hydrogen sulfide, the rest is air. The test duration - 15 hours. During the work activity of the catalyst decreased by 6% relative. When this catalyst was provided with the necessary degree of purification within the MPC not only from carbon monoxide, and hydrogen sulfide. The concentration of hydrogen sulfide in the air after cleaning was 1 mg/m3.

Thus, the proposed catalyst provides effective cleaning gas mixture in a wide range of the original content of carbon monoxide and in the presence of the purified gas mixture of sulfur-containing impurities connections.

Table 1
Number exampleComposition, %Test conditionsThe results of the tests
PdCl2 CuCl2PcMPolynuclear alcoholThe content in the source DHWt °CHumidity, % Rel.The CO content after treatment, mg/m3The degree of conversion of CO, %
%mg/m3
20,807,10PcFe, 0,10Glycerin, 3,001,0021501599,85
31,127,11PcFe, 0,10Ethylene glycol,1,001,002170699,94
42,387,06PcFe, 1,00Glycerin, 0,501,002070199,99
52,413,09PcFe, 1,00Glycerin, 0,501,002130199,99
61,127,09PcFe, 1,00Glycerin, 3,001,002190 4of 99.96
70,807,05PcFe, 1,00Glycerin, 3,001,0021921599,85
82,387,06PcCo, 0,10Ethylene glycol, 3,001002150397,00
91,127,11PcCo, 0,50Glycerin, 3,0010520509At 91.43
100,807,13PcFe, 0,60Ethylene glycol,1,0010320201090,30
112,405,08PcFe, 0,60Diethylene glycol, 0,501002220397,00
122,424,08PcCo, 0,60Glycerin, 3,0010022502for 98.00
132,378,03PcFe, 0,10Glycerin, 3,0 1062160892,45
142,364,42aPcFe, 0,10Diethylene glycol, 0,501022275298,03
152,354,05bPcCo, 0,10Diethylene glycol, 0,5010021952for 98.00
16c2,54to 11.79PcFe, 0,40Glycerin, 0,501102095595,45
andthe catalyst, in addition to the table amount of CuCl2contains 5,22% CuSO4< / br>
bthe catalyst, in addition to the table amount of CuCl2contains 5,03% CuBr2< / br>
withthe catalyst prepared using palladium bromide and copper bromide.

The catalyst for purification of air from the carbon monoxide containing deposited on a porous carrier salt, palladium salt of copper and a promoter, characterized in that as a promoter it contains phtalocyanines complex of iron or cobalt and ecomny alcohol in the following ratio of components, wt.%:

Salt of palladium0,80-2,54
Salt of copper3,09-to 11.79
Phtalocyanines complex
iron or cobalt0,10-1,00
Polynuclear alcohol0,50-3,00
Aluminium oxideRest



 

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