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 palladium||0,80-2,54|
|Salt of copper||3,09-to 11.79|
|Phtalocyanines complex of iron or cobalt||0,10-1,00|
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.
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).
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.
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.
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.
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.
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.
|Number example||Composition, %||Test conditions||The results of the tests|
|PdCl2||CuCl2||PcM||Polynuclear alcohol||The content in the source DHW||t °C||Humidity, % Rel.||The CO content after treatment, mg/m3||The degree of conversion of CO, %|
|2||0,80||7,10||PcFe, 0,10||Glycerin, 3,00||1,00||21||50||15||99,85|
|3||1,12||7,11||PcFe, 0,10||Ethylene glycol,1,00||1,00||21||70||6||99,94|
|4||2,38||7,06||PcFe, 1,00||Glycerin, 0,50||1,00||20||70||1||99,99|
|5||2,41||3,09||PcFe, 1,00||Glycerin, 0,50||1,00||21||30||1||99,99|
|6||1,12||7,09||PcFe, 1,00||Glycerin, 3,00||1,00||21||90||4||of 99.96|
|7||0,80||7,05||PcFe, 1,00||Glycerin, 3,00||1,00||21||92||15||99,85|
|8||2,38||7,06||PcCo, 0,10||Ethylene glycol, 3,00||100||21||50||3||97,00|
|9||1,12||7,11||PcCo, 0,50||Glycerin, 3,00||105||20||50||9||At 91.43|
|10||0,80||7,13||PcFe, 0,60||Ethylene glycol,1,00||103||20||20||10||90,30|
|11||2,40||5,08||PcFe, 0,60||Diethylene glycol, 0,50||100||22||20||3||97,00|
|12||2,42||4,08||PcCo, 0,60||Glycerin, 3,00||100||22||50||2||for 98.00|
|13||2,37||8,03||PcFe, 0,10||Glycerin, 3,0||106||21||60||8||92,45|
|14||2,36||4,42a||PcFe, 0,10||Diethylene glycol, 0,50||102||22||75||2||98,03|
|15||2,35||4,05b||PcCo, 0,10||Diethylene glycol, 0,50||100||21||95||2||for 98.00|
|16c||2,54||to 11.79||PcFe, 0,40||Glycerin, 0,50||110||20||95||5||95,45|
|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 palladium||0,80-2,54|
|Salt of copper||3,09-to 11.79|
|iron or cobalt||0,10-1,00|
FIELD: production of catalytic neutralizers.
SUBSTANCE: high-efficiency catalytic neutralizer has internal and external layers on inert carrier which contain noble metals of platinum group deposited on materials of base and oxygen-accumulating components. Inner layer of proposed catalytic neutralizer contains platinum deposited on first base and first oxygen-accumulating component and its external layer contains platinum and rhodium deposited on second base only; this second layer contains additionally second oxygen-accumulating component. Production of catalytic neutralizer includes application of coat on carrier made from composition containing powder-like materials including first material of base and first oxygen-accumulating component followed by drying, calcining, immersing the carrier with coat in solution of platinum precursor; coat is calcined and external layer is applied over previous layer. Specification describes two more versions of production of catalytic neutralizer.
EFFECT: enhanced ability of catalytic neutralizer for reduction of catalytic activity after aging due to discontinuation of delivery of fuel.
24 cl, 1 dwg, 11 tbl, 5 ex, 3 ex
FIELD: catalysts of selective hydrogenation of alkynes of C4 fractions.
SUBSTANCE: proposed catalyst contains 1-30 mass-% of copper used as first active component, 0.001-5 mass-% of palladium used as second active component, at least 0.001-6 mass-% of one metal selected from Al, Pt, Pb, Mn, Co, Ni, Cr, Bi, Zr and Mo as co-catalyst; the remainder being one carrier selected from aluminum oxide, silicon dioxide and titanium oxide. Method of production of catalyst includes impregnation of carrier calcined preliminarily with solutions of active components depending on their content in catalyst. Alkynes are removed from C4 fractions enriched with alkynes by means of selective hydrogenation with the use of said catalyst.
EFFECT: enhanced selectivity and stability of catalyst.
31 cl, 2 tbl, 13 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: cobalt-based catalyst precursor is prepared by impregnation of porous catalyst carrier particles with cobalt salt followed by partial drying and subsequent calcination of impregnated carrier, after which calcined product is partially reduced, impregnated with cobalt salt, partially dried and finally calcined. Preparation of Fischer-Tropsch catalyst comprises similar preparation of precursor thereof and reduction of the latter.
EFFECT: increased catalytic activity.
12 cl, 3 dwg, 1 tbl, 2 ex
FIELD: industrial organic synthesis.
SUBSTANCE: invention provides a method for preparing improved oxirane hydroformylation catalyst, improved oxirane hydroformylation catalyst, and single-stage process for production of 1,3-diol in presence of such catalyst. Preparation of catalyst comprises preparing complex A by contacting ruthenium(0) compound with di-tertiary phosphine ligand and preparing complex B via redox reaction of complex A with cobalt(0) carbonyl compound. Single-stage 1,3-diol production process involves reaction of oxirane with synthesis gas under hydroformylation conditions in inert solvent in presence of aforesaid catalyst, where recovery of product is preferably accomplished through separation of product-rich phase.
EFFECT: reduced number of stages to a single one or increased yield of 1,3-diol without by-products and preserved catalytic activity after catalyst regeneration operation.
10 cl, 3 dwg, 6 tbl, 21 ex
FIELD: petrochemical processes catalysts.
SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on granulated halumine may further contain promoters selected from oxides ZrO2 and HfO2 and metals Ru, Pd, and Pt.
EFFECT: increased selectivity and productivity.
2 cl, 3 tbl, 2 ex
FIELD: petrochemical process catalysts.
SUBSTANCE: fischer-Tropsch process catalyst constituted by cobalt deposited on aluminum metal may additionally contain promoters selected from oxides ZrO2, La2O3, K2O and metals Re, Ru, Pd, and Pt.
EFFECT: increased heat conductivity and selectivity.
2 cl, 2 tbl, 2 ex
FIELD: selective oxidation of carbon monoxide in hydrogen-containing stream.
SUBSTANCE: invention relates to method for selective oxidation of carbon monoxide to carbon dioxide in raw material containing hydrogen and carbon monoxide in presence of catalyst comprising platinum and iron. Catalyst may be treated with acid. Certain amount of free oxygen is blended with mixture containing hydrogen and carbon monoxide to provide second gaseous mixture having elevated ratio of oxygen/carbon monoxide. Second gaseous mixture is brought into contact with catalyst, containing substrate impregnated with platinum and iron. Carbon monoxide in the second gaseous mixture is almost fully converted to carbon dioxide, i.e. amount of carbon monoxide in product stream introduced into combustion cell is enough small and doesn't impact on catalyst operation characteristics.
EFFECT: production of hydrogen fuel for combustion cell with industrial advantages.
13 cl, 1 tbl, 4 ex
FIELD: chemical refining of waste gasses.
SUBSTANCE: the invention is dealt with a method of purification of waste gasses of heating and power stations from carbon dioxide by introduction in the waste gas stream of products of incineration of hydrocarbon fuel of an alkaline solution. At that the alkaline solution is fed in a dispersed form into the upstream of the waste gasses moving in a turbulent mode in the space of the stalk of the heating and power station. In the capacity of the alkaline solution they use circulating water of ash removal of the heating and power station. A dispersed alkaline solution is fed into the base part of the stalk of the heating and power station. Before use of the circulating water of ash removal increase its alkalinity by mixing it with the ash from consequent separation of the solution and the ash residue by settling and filtration. At that alkali is extracted from ash into the water. The invention ensures increased completeness and speed of interaction of the components at the expense of use of energy of the purified stream of the waste gasses.
EFFECT: the invention ensures increased completeness and speed of interaction of the components due to use of energy of the purified stream of the waste gasses.
FIELD: gas treatment.
SUBSTANCE: invention is intended for fine purification of gases with removal of carbon dioxide at elevated pressures, in particular in hydrogen or ammonia production processes. Absorbent is an aqueous solution containing N-methyldiethanolamine, piperazine, potassium carbonate, and morpholine. Invention achieves reduced equilibrium pressure and increased carbon dioxide absorption at low degrees of carbonization (as low as 0.1 mole CO2 per mole tertiary amine) without appreciable N-methyldiethanolamine degradation rate.
EFFECT: enhanced carbon dioxide absorption efficiency.
2 dwg, 6 tbl, 2 ex
FIELD: gas treatment.
SUBSTANCE: invention relates to adsorption separation of gases and provides carbon dioxide absorbent, which is prepared by impregnating porous alumina with potassium carbonate, alumina having been preliminarily treated with alkali solution, in particular solution of alkali metal hydroxides and/or carbonates. Alkali treatment is carried out at temperature above 40оС. Method of removing carbon dioxide from gas mixture, including adsorption separation of carbon dioxide from atmospheric air in cyclic processes under thermal regeneration or short-cycle heating-free adsorption conditions, is characterized by that process is conducted at 20 to 200оС with above indicated absorber.
EFFECT: increased dynamic capacity of absorber and increased carbon dioxide absorption velocity.
5 cl, 2 dwg, 9 ex